Gemini surfactant and their use

ABSTRACT

Disclosed herein are gemini surfactants, and methods for making and using these gemini surfactants. These gemini surfactants may be incorporated in paints and coatings to provide hydrophilic and/or self-cleaning properties.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a U.S. National Stage filing under 35 U.S.C. § 371of International Application No. PCT/US2013/072619, filed on Dec. 2,2013, entitled “NOVEL GEMINI SURFACTANTS AND THEIR USE,” which isincorporated herein by reference in its entirety.

BACKGROUND

Surfactants are compounds composed of both hydrophilic and hydrophobicor lipophilic groups. In view of their dual hydrophilic and hydrophobicnature, surfactants tend to concentrate at the interfaces of aqueousmixtures; the hydrophilic part of the surfactant orients itself towardsthe aqueous phase and the hydrophobic part orients itself away from theaqueous phase. Due to these properties, surfactants can be used asemulsifiers for emulsion polymerization reactions during the manufactureof paints, Surfactants, in addition, improve wetting of the substrate bythe coating, and wetting of the pigment by the resin. The presence of asurfactant can also affect the mechanical, chemical, freezing, andstorage stability of the polymers in paints and emulsions. Additionally,surfactants may also affect the water, moisture, heat resistance, andadhesiveness of a polymer film. As such, both ionic and non-ionicsurfactants may be used in coating compositions.

Gemini surfactants (sometimes referred to as dimeric surfactants) are anew class of surfactants that have two or more hydrophilic groups andtwo or more hydrophobic groups in the molecules. Typically, geminisurfactants have low critical micelle concentrations, and may be used inlower amounts than conventional surfactants. Gemini surfactants can beten to a thousand times more surface-active than conventionalsurfactants with similar but single, hydrophilic and hydrophobic groupsin the molecules. Further, gemini surfactants may be anionic, cationic,nonionic or zwitterionic.

In paint industry, leaching of surfactants, breaking down of emulsionsystem, and freezing represent major problems in terms of maintainingthe quality and durability of the paint. These problems can be overcomeby developing new and efficient class of surfactants that are polymericand self-emulsifying.

SUMMARY

Disclosed herein are novel gemini surfactants that are non-leachable,have high surfactant efficiency, and form stable emulsions. These geminisurfactants may he used in coating compositions and emulsions to providehydrophilic, self-cleaning properties when applied on a surface.

The current disclosure is directed to novel Gemini surfactants. In oneembodiment, a compound is of formula I:

-   -   wherein A¹ is —H, —N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂,        —NH—CH₂—CH₂—OH, —N⁺(CH₂—CH₂—OH)₃.X⁻, —O—Z—CH₃, —N⁺[Z—CH₃]₃.X⁻,        —O—C(═O)—COO⁻.Na⁺, —N⁺(—CH₃)₂—Z—CH₃.X⁻, or salts thereof;    -   A² is —H, —N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂, —N⁺H₃.X⁺, —N[Z—CH₃]₂,        —NH—CH₂—CH₂—OH, —N⁺(CH₂—CH₂—OH)₃.X⁻, —O—Z—CH₃, —N⁺(Z—CH₃)₃.X⁻,        —O—C(═O)—COO⁻.Na⁺, —N⁺(—CH₃)₂—Z—CH₃.X⁻, or salts thereof;    -   A³ is —N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂, —N⁺H₃.X⁺, —N[Z—CH₃]₂,        —NH—CH₂—CH₂—OH, —N⁺(CH₂—CH₂—OH)₃.X⁻, —O—Z—CH₃, —N⁺(Z—CH₃)₃.X⁻,        —O—C(═O)—COO⁻.Na⁺, —N⁺(—CH₃)₂—Z—CH₃.X⁻, or salts thereof;    -   A⁴ is —N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂,        —NH—CH₂—CH₂—OH, —N⁺(CH₂—CH₂—OH)₃.X⁻, —O—Z—CH₃, —N⁺(Z—CH₃)₃.X⁻,        —O—C(═O)—COO⁻Na⁺, —N⁺(—CH₃)₂—Z—CH₃.X⁻, or salts thereof;    -   each Z is, independently, C₁-C₂₅ alkylene, C₁-C₂₅ substituted        alkylene, C₆-C₂₅ arylene, C₆-C₂₅ substituted arylene, C₂-C₂₅        alkenylene, C₂-C₂₅ substituted alkenylene, C₂-C₂₅ alkynylene,        C₂-C₂₅ substituted alkynylene, or absent;    -   Q is —C(═O)—, —CH₂—CH₂—, —CH₂—(CH₂)_(k)—CH₂—, —C(═O)—NH—C(═O)—,        or polyurea, where k is an integer from 1 to 10; and    -   X is Cl, Br, F, I, or OH, and    -   wherein at least one of A¹, A², A³, and A⁴ is hydrophilic, and        at least one of A¹, A², A³, and A⁴ is hydrophobic.

In another embodiment, a compound is of formula II:

-   -   wherein each A⁵ is, independently, —H, —O—C(═O)—Z—CH₃,        —N(—CH₃)—Z—CH₃, —O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH,        —O—SO₃H, —O—PO₃H₂, —N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂,        —NH—CH₂—CH₂—OH, —N—(CH₂—CH₂—OH)₂, —N⁺(CH₂—CH₂—OH)₃.X⁻, —O—Z—CH₃,        —N⁺(Z—CH₃)₃.X⁻, —O—C(═O)—COO⁻.Na⁺, or salts thereof;    -   each A⁶ is, independently, —H, —O—C(═O)—Z—CH₃, —N(—CH₃)—Z—CH₃,        —O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH, —O—SO₃H, —O—PO₃H₂,        —N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺H₃.X, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH,        —N—(CH₂—CH₂—OH)₂, —N⁺(CH₂—CH₂—OH)₃.X⁻, —O—Z—CH₃, —N⁺(Z—CH₃)₃.X⁻,        —O—C(═O)—COO⁻.Na⁺, or salts thereof;    -   each A⁷ is, independently, —O—C(═O)—Z—CH₃, —N(—CH₃)—Z—CH₃,        —O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH, —O—SO₃H, —O—PO₃H₂,        —N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH,        —N—(CH₂—CH₂—OH)₂, —N⁺(CH₂—CH₂—OH)₃.X⁻, —O—Z—CH₃, —N⁺(Z—CH₃)₃.X⁻,        —O—C(═O)—COO⁻.Na⁺, or salts thereof;    -   each Z is, independently, C₁-C₂₅ alkylene, C₁-C₂₅ substituted        alkylene, C₆-C₂₅ arylene, C₆-C₂₅ substituted arylene, C₂-C₂₅        alkenylene, C₂-C₂₅ substituted alkenylene, C₂-C₂₅ alkynylene,        C₂-C₂₅ substituted alkynylene, or absent; and    -   X is Cl, Br, F, I, or OH, and    -   wherein at least one of A⁵, A⁶, and A⁷ is hydrophilic, and at        least one of A⁵, A⁶, and A⁷ is hydrophobic.

In an additional embodiment, a compound is of formula III:

-   -   wherein    -   a is an integer from 1 to 10;    -   R¹ is —CH₂—N(—CH₃)—Z—CH₃, —C(═O)—CH₂—CH₂—COOH, —C(═O)—CH₂—COOH,        —SO₃H, —PO₃H₂, —CH₂—N[CH₂—N⁺(CH₃)₃.X⁻]₂,        —CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃.X⁻, —CH₂—CH(—OH)—CH₂—N[Z—CH₃]₂,        —CH₂—CH(—OH)—CH₂—NH—CH₂—CH₂—OH,        —CH₂—CH(—OH)—CH₂—N—(CH₂—CH₂—OH)₂,        —CH₂—CH(—OH)—CH₂—N⁺(CH₂—CH₂—OH)₃.X⁻,        —CH₂—CH(—OH)—CH₂—N⁺(Z—CH₃)₃.X⁻, —CH₂—COO⁻.Na⁺, or salts thereof;    -   each R² is, independently, —CH₂—N(—CH₃)—Z—CH₃,        —C(═O)—CH₂—CH₂—COOH, —C(═O)—CH₂—COOH, —SO₃H, —PO₃H₂,        —CH₂—N[CH₂—N⁺(CH₃)₃.X⁻]₂, —CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃.X⁻,        —CH₂—CH(—OH)—CH₂—N[Z—CH₃]₂, —CH₂—CH(—OH)—CH₂—NH—CH₂—CH₂—OH,        —CH₂—CH(—OH)—CH₂—N—(CH₂—CH₂—OH)₂,        —CH₂—CH(—OH)—CH₂—N⁺(CH₂—CH₂—OH)₃.X⁻,        —CH₂—CH(—OH)—CH₂—N⁺(Z—CH₃)₃.X⁻, —CH₂—COO⁻.Na⁺, or salts thereof;    -   R³ is —CH₂—N(—CH₃)—Z—CH₃, —C(═O)—CH₂—CH₂—COOH, —C(═O)—CH₂—COOH,        —SO₃H, —PO₃H₂, —CH₂—N[CH₂—N⁺(CH₃)₃.X⁻]₂,        —CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃.X⁻, —CH₂—CH(—OH)—CH₂—N[Z—CH₃]₂,        —CH₂—CH(—OH)—CH₂—NH—CH₂—CH₂—OH,        —CH₂—CH(—OH)—CH₂—N—(CH₂—CH₂—OH)₂,        —CH₂—CH(—OH)—CH₂—N⁺(CH₂—CH₂—OH)₃.X⁻,        —CH₂—CH(—OH)—CH₂—N⁺(Z—CH₃)₃.X⁻, —CH₂—COO⁻Na⁺, or salts thereof;    -   R⁴ is —N(—CH₃)—Z—CH₃, —O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH,        —O—SO₃H, —O—PO₃H₂, —N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂,        —NH—CH₂—CH₂—OH, —N—(CH₂—CH₂—OH)₂, —N⁺(CH₂—CH₂—OH)₃.X⁻,        —N⁺(Z—CH₃)₃.X⁻, —Z—CH₃, or salts thereof;    -   each R⁵ is, independently, —N(—CH₃)—Z—CH₃,        —O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH, —O—SO₃H, —O—PO₃H₂,        —N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH,        —N—(CH₂—CH₂—OH)₂, —N⁺(CH₂—CH₂—OH)₃.X⁻, —N⁻(Z—CH₃)₃.X⁻, —Z—CH₃,        or salts thereof;    -   R⁶ is —N(—CH₃)—Z—CH₃, —O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH,        —O—SO₃H, —O—PO₃H₂, —N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂,        —NH—CH₂—CH₂—OH, —N—(CH₂—CH₂—OH)₂, —N⁺(CH₂—CH₂—OH)₃.X⁻,        —N⁺(Z—CH₃)₃.X⁻, —Z—CH₃, or salts thereof;

-   each Z is independently, alkylene, C₁-C₂₅ substituted alkylene,    C₁-C₂₅ substituted alkylene, C₆-C₂₅ arylene, C₆-C₂₅ substituted    arylene, C₂-C₂₅ alkenylene, C₂-C₂₅ substituted alkenylene, C₂-C₂₅    alkynylene, C₂-C₂₅ substituted alkynylene, or absent; and    -   X is Cl, Br, F, I, or OH, and    -   wherein at least one of R¹, R², R³, R⁴, R⁵, and R⁶ is        hydrophilic, and at least one of R¹, R², R³, R⁴, R⁵, and R⁶ is        hydrophobic.

In another embodiment, a compound is of formula IV:

-   -   wherein    -   R⁷ is —N(—CH₃)—Z—CH₃, —N[CH₂—N⁺(CH₃)₃X⁻]₂, —N⁺(CH₃)₃.X⁻,        —N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH, —N—(CH₂—CH₂—OH)₂,        —N(CH₂—CH₂—OH)₃.X⁻, —N—(CH₂—CH₂—COOH)₂, or salts thereof;    -   R⁸ is —OH, —O—C(═O)—Z—CH₃, —N(—CH₃)—Z—CH₃,        —O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH, —N[CH₂—N⁺(CH₃)₃.X⁻]₂,        —N⁺H₃.X⁻, —N[Z—CH₃]₂, —N⁺(Z—CH₃)₃.X⁻, —NH—CH₂—CH₂—OH,        —N—(CH₂—CH₂—OH)₂, —N⁺(CH₂—CH₂OH)₃.X⁻, —O—Z—CH₃, or salts        thereof;    -   R⁹ is —H, —CH₂—O—C(═O)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃,        —CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,        —CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, —CH₂—N—(CH₂—CH₂—OH)₂,        —CH₂—N⁺(CH₂—CH₂—OH)₃, —CH₂—O—Z—CH₃, —CH₂—N⁺(Z—CH₃)₃.X⁻, or salts        thereof;    -   R¹⁰ is —H, —CH₂—O—C(═O)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃,        —CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,        —CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, —CH₂—N—(CH₂—CH₂—OH)₂,        —CH₂—N⁺(CH₂—CH₂—OH)₃, —CH₂—O—Z—CH₃, —CH₂—N⁺(Z—CH₃)₃.X⁻, or salts        thereof;    -   R¹¹ is —H, —CH₂—O—C(═O)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃,        —CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,        —CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, —CH₂—N—(CH₂—CH₂—OH)₂,        —CH₂—N⁺(CH₂—CH₂—OH)₃, —CH₂—O—Z—CH₃, —CH₂—N⁺(Z—CH₃)₃.X⁻, or salts        thereof;    -   R¹² is —H, —CH₂—O—C(═O)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃,        —CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,        —CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, —CH₂—N—(CH₂—CH₂—OH)₂,        —CH₂—N⁺(CH₂—CH₂—OH)₃, —CH₂—O—Z—CH₃, —CH₂—N⁺(Z—CH₃)₃.X⁻, or salts        thereof;    -   R¹³ is —OH, —O—C(═O)—Z—CH₃, —N(—CH₃)—Z—CH₃,        —O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH, —N[CH₂—N⁺(CH₃)₃.X⁻]₂,        —N⁺H₃.X⁻, —N[Z—CH₃]₂, —N⁺(Z—CH₃)₃.X⁻, —NH—CH₂—CH₂—OH,        —N—(CH₂—CH₂—OH)₂, —N⁺(CH₂—CH₂—OH)₃.X⁻, —O—Z—CH₃, or salts        thereof;    -   R¹⁴ is —N(—CH₃)—Z—CH₃, —N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺(CH₃)₃.X⁻,        —N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH, —N—(CH₂—CH₂—OH)₂,        —N⁺(CH₂—CH₂—OH)₃.X⁻, —N—(CH₂—CH₂—COOH)₂, or salts thereof;    -   E is —CH₂—, —C(CH₃)₂—, —S—, —S(═O)₂—, —S(═O)—, —CH(CCl₃)—,        —C(Cl)₂—, —O—, or —C(F)₂—;

-   each Z is, independently, C₁-C₂₅ alkylene, C₁-C₂₅ substituted    alkylene, C₆-C₂₅ arylene, C₆-C₂₅ substituted arylene, C₂-C₂₅    alkenylene, C₂-C₂₅ substituted alkenylene, C₂-C₂₅ alkynylene, C₂-C₂₅    substituted alkynylene, or absent; and    -   X is Cl, Br, F, I, or OH, and    -   wherein at least one of R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, and R¹⁴        is hydrophilic, and at least one of R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²,        R¹³, and R¹⁴ is hydrophobic.

In a further embodiment, a compound is of formula V:

-   -   wherein    -   R¹⁵ is —N(—CH₃)—Z—CH₃, —N[CH₂—N⁺(CH₃)₃X⁻]₂, —N⁺(Z—CH₃)₃.X⁻,        —N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH, —N—(CH₂—CH₂—OH)₂,        —N⁺(CH₂—CH₂—OH)₃.X⁻, —N—(CH₂—CH₂—COOH)₂, or salts thereof;    -   R¹⁶ is —H, —CH₂—O—C(═O)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃,        —CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,        —CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, —CH₂—N—(CH₂—CH₂—OH)₂,        —CH₂—N⁺(CH₂—CH₂—OH)₃, —CH₂—O—Z—CH₃, —CH₂—N⁺(Z—CH₃)₃.X⁻,        —CH₂—O—CH₂—CHOH—CH₂—N(Z—CH₃)₂, or salts thereof;    -   R¹⁷ is —H, —CH₂—O—C(═O)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃,        —CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,        —CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, —CH₂—N—(CH₂—CH₂—OH)₂,        —CH₂—N⁺(CH₂—CH₂—OH)₃, —CH₂—O—Z—CH₃, —CH₂—N⁺(Z—CH₃)₃.X⁻,        —CH₂—O—CH₂—CHOH—CH₂—N(Z—CH₃)₂, or salts thereof;    -   R¹⁸ is —CH—O—C(═O)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃,        —CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,        —CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, —CH₂—N—(CH₂—CH₂—OH)₂,        —CH₂—N⁺(CH₂—CH₂—OH)₃, —CH₂—O—Z—CH₃, —CH₂—N⁺(Z—CH₃)₃.X⁻,        —CH₂—O—CH₂—CHOH—CH₂—N(Z—CH₃)₂, or salts thereof;    -   each Z is, independently, C₁-C₂₅ alkylene, C₁-C₂₅ substituted        alkylene, C₆-C₂₅ arylene, C₆-C₂₅ substituted arylene,        alkenylene, C₂-C₂₅ substituted alkenylene, C₂-C₂₅ alkynylene,        C₂-C₂₅ substituted alkynylene, or absent; and    -   X is Cl, Br, F, I, or OH, and    -   wherein at least one of R¹⁵, R¹⁶, R¹⁷, and R¹⁸ is hydrophilic,        and at least one of R¹⁵, R¹⁶, R¹⁷, and R¹⁸ is hydrophobic.

In yet another embodiment, a composition may include any one or more ofthe compounds described herein.

In a further embodiment, a method of making a compound of formula I mayinvolve contacting any one of urea, biuret, or alkylene diamine withformaldehyde to form a hydroxymethyl compound; and contacting thehydroxymethyl compound with a dimethyl alkyl amine.

In an additional embodiment, a method of making a compound of formula IImay involve contacting melamine with formaldehyde to form ahydroxymethyl melamine derivative; contacting the hydroxymethyl melaminederivative diethanolamine to form a diethanol melamine derivative; andcontacting the diethanol melamine derivative with an alkyl halide.

In a further embodiment, a method of making a compound of formula IIImay involve contacting novolac with epichlorohydrin to form anovolac-chlorohydrin derivative; contacting the novolac-chlorohydrinderivative with any one of diethanolamine or triethylamine to form anovolac derivative; and contacting the novolac derivative with an alkylchloride.

In another embodiment, a method of making a compound of formula IV mayinvolve contacting a bisphenol compound with epichlorohydrin andformaldehyde to form a tetramethylol bisphenol derivative; andcontacting the tetramethylol bisphenol derivative with any one of thefollowing: a mixture of trimethylamine and N,N,N,-trialkyl amine, amixture of diethanol amine and N,N,N,-trialkyl amine, and a mixture ofdisodium propionate amine and N,N,N,-trialkyl amine.

In yet an another embodiment, a method of making a compound of formula Vmay involve contacting a resol with epichlorohydrin to form aresol-chlorohydrin derivation; and contacting the resol-chlorohydrinderivative with any one of the following: a mixture of triethylamine andN,N,N,-trialkyl amine, a mixture of diethanol amine and N,N,N,-trialkylamine, a mixture of disodium propionate amine and N,N,N,-trialkyl amine.

In a further embodiment, a method of coating a substrate may involveapplying a coating composition to the substrate, wherein the coatingcomposition comprises one or more compounds of formula I-V.

DETAILED DESCRIPTION

This disclosure is not limited to the particular systems, devices andmethods described, as these may vary. The terminology used in thedescription is for the purpose of describing the particular versions orembodiments only, and is not intended to limit the scope.

“Alkyl” means a saturated hydrocarbon group which is straight-chained orbranched. An alkyl group can contain from 1 to 20 carbon atoms, from 2to 20 carbon atoms, from 1 to 10 carbon atoms, from 2 to 10 carbonatoms, from 1 to 8 carbon atoms, from 2 to 8 carbon atoms, from 1 to 6carbon atoms, from 2 to 6 carbon atoms, from 1 to 4 carbon atoms, from 2to 4 carbon atoms, from 1 to 3 carbon atoms, or 2 or 3 carbon atoms,Examples of alkyl groups include, but are not limited to, methyl (Me),ethyl (Et), propyl (for example, n-propyl and isopropyl), butyl (forexample, n-butyl, t-butyl, isobutyl), pentyl (for example, n-pentyl,isopentyl, neopentyl), hexyl, isohexyl, heptyl, 4,4 dimeklpentyl, octyl,2,2,4-trimeklpentyl, nonyl, decyl, undecyl, dodecyl, 2-methyl-1-propyl,2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl,2-methyl-1-pentyl, 2,2-dimethyl-1-propyl, 3-methyl-1-pentyl,4-methyl-1-pentyl, 2-methyl-2-penty 3-methyl-2-pentyl,4-methyl-2-pentyl, 2,2-dimethyl-1-butyl, 3,3 -dimethyl-1-butyl2-ethyl-1-buty 1, and the like.

“Substituted alkyl” refers to an alkyl as just described in which one ormore hydrogen atoms attached to carbon of the alkyl is replaced byanother group, such as halogen, aryl, substituted aryl, cycloalkyl,substituted cycloalkyl, and combinations thereof. Suitable substitutedalkyls include, for example, benzyl and trifluoromethyl.

“Alkylene” refers to a bivalent alkyl moiety having the general formula—(CH₂)_(n)—, where n is from about 1 to about 25, about 1 to about 20,or about 4 to about 20. By bivalent, it is meant that the group has twoopen sites each of which bonds to another group. Non-lirniting examplesinclude methylene, ethylene, trimethylene, pentamethylene, andhexamethylene. Alkylene groups can be substituted or unsubstituted,linear or branched bivalent alkyl groups.

“Alkenyl” means a straight or branched alkyl group having one or moredouble carbon-carbon bonds and 2-20 carbon atoms, including, but notlimited to, ethenyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl,1-butenyl, 2-butenyl, and the like. In some embodiments, the alkenylchain is from 2 to 10 carbon atoms in length, from 2 to 8 carbon atomsin length, from 2 to 6 carbon atoms in length, or from 2 to 4 carbonatoms in length.

“Alkenylene” refers to a divalent alkenyl moiety, meaning the alkenyimoiety is attached to the rest of the molecule by a divalent linkage.

“Alkynyl” means a straight or branched alkyl group having one or moretriple carbon-carbon bonds and 2-20 carbon atoms, including, but notlimited to, acetylene, 1-propylene, 2-propylene, and the like. In someembodiments, the alkynyl chain is 2 to 10 carbon atoms in length, from 2to 8 carbon atoms in length, from 2 to 6 carbon atoms in length, or from2 to 4 carbon atoms in length.

“Alkynylene” refers to a divalent alkynyl moiety, meaning the alkynylmoiety is attached to the rest of the molecule by a divalent linkage.

“Arylene” means a bivalent aryl group that links one group to anothergroup in a molecule. Arylene groups may be substituted or unsubstituted.

Disclosed herein are gemini surfactants, and methods of making suchsurfactants, These gemini surfactants may be used in variousapplications, such as in coating compositions, emulsions, demulsifyingagents, phase transfer catalysts, dispersants, and defoamers.

In some embodiments, a compound is of formula I:

-   -   wherein A¹ may be —H, —N[CH₂—N⁺(Z—CH₃)₃.X⁻], —N[Z—CH₃]₂,        —NH—CH₂—CH₂OH, —N¹(CH₂—CH₂—OH)₃.X⁻, —O—Z—CH₃, —N¹[Z—CH₃]₃.X⁻,        —O—C(═O)—COO⁻.Na⁺, —N⁺(—CH₃)₂—Z—CH₃.X⁻, or salts thereof. In        some embodiments, A¹ may —H, —N[CH₂—N⁺(Z—CH₃)₃.X⁺]₂, —N⁺H₃.X⁻,        —N[Z—CH₃]₂, —NH—CH₂CH₂—OH, —N⁺(CH₂—CH₂—OH)₃.X⁻, or —O—Z—CH₃. In        some embodiments, A¹ may be —H, —N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂,        —N⁺H₃.X⁻, —N[Z—CH₃]₂, or —NH—CH₂—CH₂OH.

In some embodiments, A² is —H, —N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂, —N⁺H₃.X⁺,—N[Z—CH₃]₂, —NH—CH₂—CH₂—OH, —N⁺(CH₂—CH₂—OH)₃.X⁻, —O—Z—CH₃,—N⁺(Z—CH₃)₃.X⁻, —O—C(═O)—COO⁻.Na⁺, —N⁺(—CH₃)₂—Z—CH₃.X⁻, or saltsthereof. In some embodiments, A² may be —H, —N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂,—N⁺H₃.X⁺, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH, —N⁺(CH₂—CH₂—OH)₃.X⁻, or —O—Z—CH₃.In some embodiments, A² may be —H, —N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂, —N⁺H₃.X⁺,—N[Z—CH₃]₂, or —NH—CH₂—CH₂—OH.

In some embodiments, A³ is may be —N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂, —N⁺H₃.X⁺,—N[Z—CH₃]₂, —NH—CH₂—CH₂—OH, —N⁺(CH₂—CH₂—OH)₃.X⁻, —O—Z—CH₃,—N⁺(Z—CH₃)₃.X⁻, —O—C(═O)—COO⁻.Na⁺, —N⁺(—CH₃)₂—Z—CH₃.X⁻, or saltsthereof. In some embodiments, A³ may be —N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂,—N⁺H₃.X⁺, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH, —N⁺(CH₂—CH₂—OH)₃.X⁻, or —O—Z—CH₃.In some embodiments, A³ may be —N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂, —N⁺H₃.X⁺,—N[Z—CH₃]₂, —NH—CH₂—CH₂—OH.

In some embodiments, A⁴ may be —N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂, —N⁺H₃.X⁺,—N[Z—CH₃]₂, —NH—CH₂—CH₂—OH, —N⁺(CH₂—CH₂—OH)₃.X⁻, —O—Z—CH₃,—N⁺(Z—CH₃)₃.X⁻, —O—C(═O)—COO⁻.Na⁺, —N⁺(—CH₃)₂—Z—, or salts thereof. Insome embodiments, A⁴ may be —N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂, —N⁺H₃.X⁺,—N[Z—CH₃]₂, —NH—CH₂—CH₂—OH, —N⁺(CH₂—CH₂—OH)₃.X⁻, or —O—Z—CH₃. In someembodiments, A⁴ may be —N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂, —N⁺H₃.X⁺, —N[Z—CH₃]₂, or—NH—CH₂—CH₂—OH.

In some embodiments, each Z may be, independently, C₁-C₂₅ alkylene,C₁-C₂₅ substituted alkylene, C₆-C₂₅ aiylene, C₆-C₂₅ substituted aiyiene,C₂-C₂₅ alkenylene, C₇-C₂₅ substituted alkenyle alkynylene. C₂-C₂₅substituted alkynylene, or absent.

In some embodiments, Q may be —C(═)—, —CH₂—CH₂—, —CH₂—(CH₂)_(k)—CH₂—,—C(═O)—NH—C(═O)—, or polyurea, where k is an integer from 1 to 10.

In some embodiments, X may he Cl, Br, F, I, or OH. In some embodiments,in the compound formula I disclosed herein, at least one of A¹, A², A³,and A⁴ may be hydrophilic, and at least one of A¹, A², A³, and A⁴ may behydrophobic.

In some embodiments, the compound of formula I may have the followingsubstitutions at each of independently, A¹, A², A³, A⁴, and Q as shownin Table 1:

TABLE 1 Q A¹ A² —C(═O)—, —H, —H, —CH₂—CH₂—, —N[CH₂—N⁺(Z—CH₃)₃•X⁻]₂,—N[CH₂—N⁺(Z—CH₃)₃•X⁻]₂, —CH₂—(CH₂)_(k)—CH₂—, —N⁺H₃•X⁻, —N⁺H₃•X⁻,—C(═O)—NH—C(═O)—, —N[Z—CH₃]₂, —N[Z—CH₃]₂, or polyurea, where k is an—NH—CH₂—CH₂—OH, —NH—CH₂—CH₂—OH, integer from 1 to 10.—N⁺(CH₂—CH₂—OH)₃•X⁻, —N⁺(CH₂—CH₂—OH)₃•X⁻, —O—Z—CH₃, —O—Z—CH₃,—N⁺[Z—CH₃]₃•X⁻, —N⁺(Z—CH₃)₃•X⁻, —O—C(═O)—COO⁻•Na⁺, —O—C(═O)—COO⁻•Na⁺,—N⁺(—CH₃)₂—Z—CH₃•X⁻, —N⁺(—CH₃)₂—Z—CH₃•X⁻, or salts thereof; or saltsthereof; —C(═O)—, —H, —H, —CH₂—CH₂—, —N[CH₂—N⁺(Z—CH₃)₃•X⁻]₂,—N[CH₂—N⁺(Z—CH₃)₃•X⁻]₂, —CH₂—(CH₂)_(k)—CH₂—, —N⁺H₃•X⁻, —N⁺H₃•X⁻,—C(═O)—NH—C(═O)—, —N[Z—CH₃]₂, —N[Z—CH₃]₂, or polyurea, where k is an—NH—CH₂—CH₂—OH, —NH—CH₂—CH₂—OH, integer from 1 to 10.—N⁺(CH₂—CH₂—OH)₃•X⁻, —N⁺(CH₂—CH₂—OH)₃•X⁻, or —O—Z—CH₃. or —O—Z—CH₃.—C(═O)— —N[Z—CH₃]₂ —N[Z—CH₃]₂ or —CH₂—(CH₂)_(k)—CH₂— or —O—Z—CH₃ or—O—Z—CH₃ —C(═O)— —N[Z—CH₃]₂ —N[Z—CH₃]₂ —C(═O)— —O—C(═O)—COO⁻•Na⁺—O—Z—CH₃ —C(═O)— —O—C(═O)—COOH —O—Z—CH₃ —C(═O)— —N[CH₂—N⁺(Z—CH₃)₃•OH⁻]₂—O—Z—CH₃ —C(═O)— —N⁺(Z—CH₃)₃•Br⁻ —O—Z—CH₃ —C(═O)—NH—C(═O)— —N[Z—CH₃]₂—N[Z—CH₃]₂ —C(═O)—NH—C(═O)— —O—C(═O)—COO⁻•Na⁺ —O—Z—CH₃ —C(═O)—NH—C(═O)——N[CH₂—N⁺(Z—CH₃)₃•OH⁻]₂ —O—Z—CH₃ —C(═O)—NH—C(═O)— —N⁺(Z—CH₃)₃•Br⁻—O—Z—CH₃ —CH₂—(CH₂)_(k)—CH₂— —N[Z—CH₃]₂ —N[Z—CH₃]₂ —CH₂—(CH₂)_(k)—CH₂——O—C(═O)—COO⁻•Na⁺ —O—Z—CH₃ —CH₂—(CH₂)_(k)—CH₂— —N[CH₂—N⁺(Z—CH₃)₃•OH⁻]₂—O—Z—CH₃ —CH₂—(CH₂)_(k)—CH₂— —N⁺(Z—CH₃)₃•Br⁻ —O—Z—CH₃ —C(═O)——N⁺(—CH₃)₂—Z—CH₃•OH⁻ —N⁺(—CH₃)₂—Z—CH₃•OH⁻ A³ A⁴ —N[CH₂—N⁺(Z—CH₃)₃•X⁻]₂,—N[CH₂—N⁺(Z—CH₃)₃•X⁻]₂, —N⁺H₃•X⁻, —N⁺H₃•X⁻, —N[Z—CH₃]₂, —N[Z—CH₃]₂,—NH—CH₂—CH₂—OH, —NH—CH₂—CH₂—OH, —N⁺(CH₂—CH₂—OH)₃•X⁻,—N⁺(CH₂—CH₂—OH)₃•X⁻, —O—Z—CH₃, —O—Z—CH₃, —N⁺(Z—CH₃)₃•X⁻, —N⁺(Z—CH₃)₃•X⁻,—O—C(═O)—COO⁻•Na⁺, —O—C(═O)—COO⁻•Na⁺, —N⁺(—CH₃)₂—Z—CH₃•X⁻,—N⁺(—CH₃)₂—Z—CH₃•X⁻, or salts thereof; or salts thereof;—N[CH₂—N⁺(Z—CH₃)₃•X⁻]₂, —N[CH₂—N⁺(Z—CH₃)₃•X⁻]₂, —N⁺H₃•X⁻, —N⁺H₃•X⁻,—N[Z—CH₃]₂, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH, —NH—CH₂—CH₂—OH,—N⁺(CH₂—CH₂—OH)₃•X⁻, —N⁺(CH₂—CH₂—OH)₃•X⁻, or —O—Z—CH₃. or —O—Z—CH₃.—N[CH₂—N⁺(CH₃)₃Br⁻]₂ —N[CH₂—N⁺(CH₃)₃Br⁻]₂ or —N⁺(Z—CH₃)₃•Br⁻ or—N⁺(Z—CH₃)₃•Br⁻ —N[CH₂—N⁺(CH₃)3•Br⁻]₂ —N[CH₂—N⁺(CH₃)3•Br⁻]₂—O—C(═O)—COO⁻•Na⁺ —O—Z—CH₃ —O—C(═O)—COOH —O—Z—CH₃—N[CH₂—N⁺(Z—CH₃)₃•OH⁻]₂ —O—Z—CH₃ —N⁺(Z—CH₃)₃•Br⁻ —O—Z—CH₃—N[CH₂—N⁺(CH₃)3•Br⁻]₂ —N[CH₂—N⁺(CH₃)3•Br⁻]₂ —O—C(═O)—COO⁻•Na⁺ —O—Z—CH₃—N[CH₂—N⁺(Z—CH₃)₃•OH⁻]₂ —O—Z—CH₃ —N⁺(Z—CH₃)₃•Br⁻ —O—Z—CH₃—N[CH₂—N⁺(CH₃)3•Br⁻]₂ —N[CH₂—N⁺(CH₃)3•Br⁻]₂ —O—C(═O)—COO⁻•Na⁺ —O—Z—CH₃—N[CH₂—N⁺(Z—CH₃)₃•OH⁻]₂ —O—Z—CH₃ —N⁺(Z—CH₃)₃•Br⁻ —O—Z—CH₃—N⁺(—CH₃)₂—Z—CH₃•OH⁻ —N⁺(—CH₃)₂—Z—CH₃•OH⁻

Examples of compounds represented by formula I include, but are notlimited to, the following compounds:

In some embodiments, a compound is of formula II:

-   -   wherein each A⁵ may be, independently, —H, —O—C(═O)—Z—CH₃,        —N(—CH₃)—Z—CH₃, —O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH,        —O—SO₃H, —O—PO₃H₂, —N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂,        —NH—CH₂—CH₂—OH, —N—(CH₂—CH₂—OH)₂, —N⁺(CH₂—CH₂—OH)₃.X⁻, —O—Z—CH₃,        —N⁺(Z—CH₃)₃.X⁻, —O—C(═O)—COO⁻.Na⁺, or salts thereof. In some        embodiments, each A⁵ may be, independently, —H, —O—C(═O)—Z—CH₃,        —N(—CH₃)—Z—CH₃, —O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH,        —O—SO₃H, —O—PO₃H₂, —N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂,        —NH—CH₂—CH₂—OH, or —N—(CH₂—CH₂—OH)₂. In some embodiments, each        A⁵ may be, independently, —H, —O—C(═O)—Z—CH₃, —N(—CH₃)—Z—CH₃,        —O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH, —O—SO₃H, —O—PO₃H₂, or        —N[CH₂—N⁺(CH₃)₃.X⁻]₂.

In some embodiments, each A⁶ may be, independently, —H, —O—C(═O)—Z—CH₃,—N(—CH₃)—Z—CH₃, —O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH, —O—SO₃H,—O—PO₃H₂, —N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH,—N—(CH₂—CH₂—OH)₂, —N⁺(CH₂—CH₂—OH)₃.X⁻, —O—Z—CH₃, —N⁺(Z—CH₃)₃.X⁻,—O—C(═O)—COO⁻.Na⁺, or salts thereof. In some embodiments, each A⁶ maybe, independently, —H, —O—C(═O)—Z—CH₃, —N(—CH₃)—Z—CH₃,—O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH, —O—SO₃H, —O—PO₃H₂,—N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH,—N—(CH₂—CH₂—OH)₂, —N⁺(CH₂—CH₂—OH)₃.X⁻, or —O—Z—CH₃. In some embodiments,each A⁶ may be independently, —H, —O—C(═O)—Z—CH₃, —N(—CH₃)—Z—CH₃,—O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH, —O—SO₃H, —O—PO₃H₂,—N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂, or —NH—CH₂—CH₂—OH.

In some embodiments, each A⁷ may be, independently, —O—C(═O)—Z—CH₃,—N(—CH₃)—Z—CH₃, —O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH, —O—SO₃H,—O—PO₃H₂, —N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH,—N—(CH₂—CH₂—OH)₂, —N⁺(CH₂—CH₂—OH)₃.X⁻, —O—Z—CH₃, —N⁺(Z—CH₃)₃.X⁻,—O—C(═O)—COO⁻.Na⁺, or salts thereof. In some embodiments, each A⁷ maybe, independently, —O—C(═O)—Z—CH₃, —N(—CH₃)—Z—CH₃,—O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH, —O—SO₃H, —O—PO₃H₂,—N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH,—N—(CH₂—CH₂—OH)₂, —N⁺(CH₂—CH₂—OH)₃.X⁻, or —O—Z—CH₃. In some embodiments,each A⁷ may be, independently, —O—C(═O)—Z—CH₃, —N(—CH₃)—Z—CH₃,—O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH, —O—SO₃H, —O—PO₃H₂,—N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂, or —NH—CH₂—CH₂—OH.

In some embodiments, each Z may be, independently, C₁-C₂₅ alkylene,C₁-C₂₅ substituted aklene. C₆-C₂₅ arylene, C₆-C₂₅ substituted arylene.C₂-C₂₅ alkenylene, C₂-C₂₅ substituted alkenylene, C₂-C₂₅ alkynylene,C₂-C₂₅ substituted aknylene, or absent.

In some embodiments, X may be Cl, Br, F, I, or OH.

In some embodiments, in compound of formula II, at least one of A⁵, A⁶,and A⁷ may be hydrophilic, and at least one of A⁵, A⁶, and A⁷ may behydrophobic.

In some embodiments, the compound of formula II may have the followingsubstitutions at each of, independently, A⁵, A⁶, and A⁷ as shown inTable 2:

TABLE 2 A⁵ A⁶ A⁷ —H, —H, —O—C(═O)—Z—CH₃, —O—C(═O)—Z—CH₃, —O—C(═O)—Z—CH₃,—N(—CH₃)—Z—CH₃, —N(—CH₃)—Z—CH₃, —N(—CH₃)—Z—CH₃, —O—C(═O)—CH₂—CH₂—COOH,—O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH,—O—C(═O)—CH₂—COOH, —O—C(═O)—CH₂—COOH, —O—SO₃H, —O—SO₃H, —O—SO₃H,—O—PO₃H₂, —O—PO₃H₂, —O—PO₃H₂, —N[CH₂—N⁺(CH₃)₃•X⁻]₂,—N[CH₂—N⁺(CH₃)₃•X⁻]₂, —N[CH₂—N⁺(CH₃)₃•X⁻]₂, —N⁺H₃•X⁻, —N⁺H₃•X⁻,—N⁺H₃•X⁻, —N[Z—CH₃]₂, —N[Z—CH₃]₂, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH,—NH—CH₂—CH₂—OH, —NH—CH₂—CH₂—OH, —N—(CH₂—CH₂—OH)₂, —N—(CH₂—CH₂—OH)₂,—N—(CH₂—CH₂—OH)₂, —N⁺(CH₂—CH₂—OH)₃•X⁻, —N⁺(CH₂—CH₂—OH)₃•X⁻,—N⁺(CH₂—CH₂—OH)₃•X⁻, —O—Z—CH₃, —O—Z—CH₃, —O—Z—CH₃, —N⁺(Z—CH₃)₃•X⁻,—N⁺(Z—CH₃)₃•X⁻, —N⁺(Z—CH₃)₃•X⁻, —O—C(═O)—COO⁻•Na⁺, —O—C(═O)—COO⁻•Na⁺—O—C(═O)—COO⁻•Na⁺, or salts thereof; or salts thereof. or salts thereof.—H, —H, —O—C(═O)—Z—CH₃, —O—C(═O)—Z—CH₃, —O—C(═O)—Z—CH₃, —N(—CH₃)—Z—CH₃,—N(—CH₃)—Z—CH₃, —N(—CH₃)—Z—CH₃, —O—C(═O)—CH₂—CH₂—COOH,—O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH,—O—C(═O)—CH₂—COOH, —O—C(═O)—CH₂—COOH, —O—SO₃H, —O—SO₃H, —O—SO₃H,—O—PO₃H₂, —O—PO₃H₂, —O—PO₃H₂, —N[CH₂—N⁺(CH₃)₃•X⁻]₂,—N[CH₂—N⁺(CH₃)₃•X⁻]₂, —N[CH₂—N⁺(CH₃)₃•X⁻]₂, —N⁺H₃•X⁻, —N⁺H₃•X⁻,—N⁺H₃•X⁻, —N[Z—CH₃]₂, —N[Z—CH₃]₂, —N[Z—CH₃]₂, or —NH—CH₂—CH₂—OH. or—NH—CH₂—CH₂—OH. or —NH—CH₂—CH₂—OH. —O—C(═O)—Z—CH₃, —O—C(═O)—Z—CH₃,—O—C(═O)—Z—CH₃, —N(—CH₃)—Z—CH₃, —N(—CH₃)—Z—CH₃, —N(—CH₃)—Z—CH₃,—O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—CH₂—COOH,—N[Z—CH₃]₂, —N(Z—CH₃]₂, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH, —NH—CH₂—CH₂—OH,—NH—CH₂—CH₂—OH, —N—(CH₂—CH₂—OH)₂, —N—(CH₂—CH₂—OH)₂, —N—(CH₂—CH₂—OH)₂,—N⁺(CH₂—CH₂—OH)₃•X⁻, —N⁺(CH₂—CH₂—OH)₃•X⁻, —N⁺(CH₂—CH₂—OH)₃•X⁻, or—O—Z—CH₃. or —O—Z—CH₃. or —O—Z—CH₃. —N⁺H₃Br⁻ —N[Z—CH₃]₂ —N[Z—CH₃]₂, or—N[CH₂—N⁺(CH₃)₃Br⁻]₂ or —O—Z—CH₃ or —O—Z—CH₃ —N⁺(Z—CH₃)₃•X⁻—O—C(═O)—Z—CH₃ —O—C(═O)—Z—CH₃ or —SO₃H or —N(—CH₃)—Z—CH₃ or—N(—CH₃)—Z—CH₃ —N(CH₂—CH₂—OH)₂ —O—C(═O)—Z—CH₃ —O—C(═O)—Z—CH₃—O—C(═O)—COO⁻•Na⁺ —O—C(═O)—Z—CH₃ —O—C(═O)—Z—CH₃ —O—SO⁻ ₃•Na⁺—O—C(═O)—Z—CH₃ —O—C(═O)—Z—CH₃ —N⁺(Z—CH₃)₃•OH⁻ —N⁺(Z—CH₃)₃•OH⁻—N⁺(Z—CH₃)₃•OH⁻ —O—PO²⁻ ₃•2Na⁺ —O—C(═O)—Z—CH₃ —O—C(═O)—Z—CH₃

Examples of compounds represented. by formula II include, but are notlimited to, the following compounds:

In some embodiments, a compound is of formula III:

-   -   wherein a is an integer from 1 to 10. In some embodiments, R¹        may be —CH₂—N(—CH₃)—Z—CH₃, —C(═O)—CH₂—CH₂—COOH, —C(═O)—CH₂—COOH,        —SO₃H, —PO₃H₂, —CH₂—N[CH₂—N⁺(CH₃)₃.X⁻]₂,        —CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃.X⁻, —CH₂—CH(—OH)—CH₂—N[Z—CH₃]₂,        —CH₂—CH(—OH)—CH₂—NH—CH₂—CH₂—OH,        —CH₂—CH(—OH)—CH₂—N—(CH₂—CH₂—OH)₂,        —CH₂—CH(—OH)—CH₂—N⁺(CH₂—CH₂—OH)₃.X⁻,        —CH₂—CH(—OH)—CH₂—N⁺(Z—CH₃)₃.X⁻, —CH₂—COO⁻.Na⁺, or salts thereof.        In some embodiments, R¹ may be —CH₂—N(—CH₃)—Z—CH₃,        —C(═O)—CH₂—CH₂—COOH, —C(═O)—CH₂—COOH, —SO₃H, —PO₃H₂,        —CH₂—N[CH₂—N⁺(CH₃)₃.X⁻]₂, —CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃.X⁻,        —CH₂—CH(—OH)—CH₂—N[Z—CH₃]₂, —CH₂—CH(—OH)—CH₂—NH—CH₂—CH₂—OH, or        —CH₂—CH(—OH)—CH₂—N—(CH₂—CH₂—OH)₂. In some embodiments, R¹ may be        —CH₂—N(—CH₃)—Z—CH₃, —C(═O)—CH₂—CH₂—COOH, —C(═O)—CH₂—COOH, —SO₃H,        —PO₃H₂, —CH₂—N[CH₂—N⁺(CH₃)₃.X⁻]₂, or        —CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃.X⁻.

In some embodiments, each R² may be, independently, —CH₂—N(—CH₃)—Z—CH₃,—C(═O)—CH₂—CH₂—COOH, —C(═O)—CH₂—COOH, —SO₃H, —PO₃H₂,—CH₂—N[CH₂—N⁺(CH₃)₃.X⁻]₂, —CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃.X⁻,—CH₂—CH(—OH)—CH₂—N[Z—CH₃]₂, —CH₂—CH(—OH)—CH₂—NH—CH₂—CH₂—OH,—CH₂—CH(—OH)—CH₂—N—(CH₂—CH₂—OH)₂, —CH₂—CH(—OH)—CH₂—N⁺(CH₂—CH₂—OH)₃.X⁻,—CH₂—CH(—OH)—CH₂—N⁺(Z—CH₃)₃.X⁻, —CH₂—COO⁻.Na⁺, or salts thereof. In someembodiments, each R² may be, independently, —CH₂—N(—CH₃)—Z—CH₃,—C(═O)—CH₂—CH₂—COOH, —C(═O)—CH₂—COOH, —SO₃H, —PO₃H₂,—CH₂—N[CH₂—N⁺(CH₃)₃.X⁻]₂, —CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃.X⁻,—CH₂—CH(—OH)—CH₂—N[Z—CH₃]₂, —CH₂—CH(—OH)—CH₂—NH—CH₂—CH₂—OH, or—CH₂—CH(—OH)—CH₂—N—(CH₂—CH₂—OH)₂. In some embodiments, each R² may be,independently, —CH₂—N(—CH₃)—Z—CH₃, —C(═O)—CH₂—CH₂—COOH, —C(═O)—CH₂—COOH,—SO₃H, —PO₃H₂, —CH₂—N[CH₂—N⁺(CH₃)₃.X⁻]₂, —CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃.X⁻,or —CH₂—CH(—OH)—CH₂—N[Z—CH₃]₂.

In some embodiments, R³ may be —CH₂—N(—CH₃)—Z—CH₃, —C(═O)—CH₂—CH₂—COOH,—C(═O)—CH₂—COOH, —SO₃H, —PO₃H₂, —CH₂—N[CH₂—N⁺(CH₃)₃.X⁻]₂,—CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃.X⁻, —CH₂—CH(—OH)—CH₂—N[Z—CH₃]₂,—CH₂—CH(—OH)—CH₂—NH—CH₂—CH₂—OH, —CH₂—CH(—OH)—CH₂—N—(CH₂—CH₂—OH)₂,—CH₂—CH(—OH)—CH₂—N⁺(CH₂—CH₂—OH)₃.X⁻, —CH₂—CH(—OH)—CH₂—N⁺(Z—CH₃)₃.X⁻,—CH₂—COO⁻.Na⁺, or salts thereof. In some embodiments, R³ may be—CH₂—N(—CH₃)—Z—CH₃, —C(═O)—CH₂—CH₂—COOH, —C(═O)—CH₂—COOH, —SO₃H, —PO₃H₂,—CH₂—N[CH₂—N⁺(CH₃)₃.X⁻]₂, —CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃.X⁻,—CH₂—CH(—OH—CH₂—N[Z—CH₃]₂, —CH₂—CH(—OH)—CH₂—NH—CH₂—CH₂—CH₂—OH, or—CH₂—CH(—OH)—CH₂—N—(CH₂—CH₂—OH)₂. In some embodiments, R³ may be—CH₂—N(—CH₃)—Z—CH₃, —C(═O)—CH₂—CH₂—COOH, —C(═O)—CH₂—COOH, —SO₃H, —PO₃H₂,—CH₂—N[CH₂—N⁺(CH₃)₃.X⁻]₂, —CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃.X⁻, or—CH₂—CH(—OH)—CH₂—N[Z—CH₃]₂.

In some embodiments, R⁴ may be —N(—CH₃)—Z—CH₃, —O—C(═O)—CH₂—CH₂—COOH,—O—C(═O)—CH₂—COOH, —O—SO₃H, —O—PO₃H₂, —N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺H₃.X⁻,—N[Z—CH₃]₂, —NH—CH₂—CH₂—OH, —N—(CH₂—CH₂—OH)₂, —N⁺(CH₂—CH₂—OH)₃.X⁻,—N⁺(Z—CH₃)₃.X⁻,—Z—Ch₃, or salts thereof. In some embodiments, R⁴ may be—N(—CH₃)—Z—CH₃, —O——C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH, —O—SO₃H,—O—PO₃H₂, —N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂OH, or—N—(CH₂—CH₂—OH)₂. In some embodiments, R⁴ may be —N(—CH₃)—Z—CH₃,—O—C(═O)—CH₂—CH₂—COOH, —O—C(═)—CH₂—COOH, —O—SO₃H, —O—PO₃H₂,—N[CH₂—N⁺(CH₃)₃.X⁻]₂, or —N⁺H₃.X⁻.

In some embodiments, each R⁵ may be, independently, —N(—CH₃)—Z—CH₃,—O—C(═O)—CH₂—CH₂—COOH, —O—C(═)——CH₂—COOH, —O—SO₃H, —O—PO₃H₂,—N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH,—N—(CH₂—OH)₂, —N⁺(CH₂—CH₂OH)₃.X⁻, —N⁺(Z—CH₃)₃.X⁻. —Z—CH₃, or saltsthereof. In some embodiments, each R⁵ may be, independently,—N(—CH₃)—Z—CH₃, —O—C(═O)—CH₂—CH₂—COOH, —O—C(═)—CH₂—COOH, —O—SO₃H,—O—PO₃H₂, —N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH, or—N—(CH₂—CH₂—OH)₂. In some embodiments, each R⁵ may be independtely,—N(—CH₃)—Z—CH₃, —O—C(═O)—CH₂—CH₂—COOH, —O—C(═)—CH₂—COOH, —O—SO₃H,—O—PO₃H₂, —N[CH₂—N⁺(CH₃)₃.X⁻]₂, or —N⁺H₃.X⁻.

In some embodiments, R⁶ may be —N(—CH₃)—Z—CH₃, —O—C(═O)—CH₂—CH₂—COOH,—O—C(═)—CH₂—COOH, —O—SO₃H, —O—PO₃H₂, —N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺H₃.X⁻,—N[Z—CH₃]₂, —NH—CH₂—CH₂—OH, —N—(CH₂—CH₂—OH)₂, —N⁺(CH₂—CH₂—OH)₃.X⁻,—N⁺(Z—CH₃)₃.X⁻, —Z—CH₃, or salts thereof. In some embodiments, R⁶ may be—N(—CH₃)—Z—CH₃, —O—C(═O)—CH₂—CH₂—COOH, —O—C(═)—CH₂—COOH, —O—SO₃H,—O—PO₃H₂, —N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH, or—N—(CH₂—CH₂—OH)₂. In some embodiment, R⁶ may be —N(—CH₃)—Z—CH₃,—O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH, —O—SO₃H, —O—PO₃H₂,—N[CH₂—N⁺(CH₃)₃.X⁻]₂, or —N⁺H₃.X⁻.

In some embodiments, each Z may be, independently, independently, C₁-C₂₅alkylene, C₁-C₂₅ substituted alkylene, C₆-C₂₅ arylene, C₆-C₂₅substituted arylene. C₁-C₂₅ alkenylene, C₂-C₂₅ substituted alkenylene,C₂-C₂₅ alkynylene, C₂-C₂₅ substituted alkynylene, or absent.

In some embodiments, X may be Cl, Br, F, I, or OH.

In some embodiments, in compound of formulat III, at least one of R¹,R², R³, R⁴, R⁵, and R⁶ is hydrophilic, and at least one of R¹, R², R³,R⁴, R⁵, and R⁶ is hydrophobic.

In some embodiments, the compound of formula III may have substitutionsat each of independently, R¹, R², R³, R⁴, R⁵, and R⁶ as shown in Table3:

TABLE 3 R¹ R² —CH₂—N(—CH₃)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃,—C(═O)—CH₂—CH₂—COOH, —C(═O)—CH₂—CH₂—COOH, —C(═O)—CH₂—COOH,—C(═O)—CH₂—COOH, —SO₃H, —SO₃H, —PO₃H₂, —PO₃H₂, —CH₂—N[CH₂—N⁺(CH₃)₃•X⁻]₂,—CH₂—N[CH₂—N⁺(CH₃)₃•X⁻]₂, —CH₂—CH(—OH)—CH₂— N⁺(CH₃)₃•X,—CH₂—CH(—OH)—CH₂— N⁺(CH₃)₃•X⁻, —CH₂—CH(—OH)—CH₂—N[Z—CH₃]₂,—CH₂—CH(—OH)—CH₂—N[Z—CH₃]₂, —CH₂—CH(—OH)—CH₂—NH—CH₂—CH₂—OH,—CH₂—CH(—OH)—CH₂—NH—CH₂—CH₂—OH, —CH₂—CH(—OH)—CH₂—N—(CH₂—CH₂—OH)₂,—CH₂—CH(—OH)—CH₂—N—(CH₂—CH₂—OH)₂, —CH₂—CH(—OH)—CH₂—N⁺(CH₂—CH₂—OH)₃•X⁻,—CH₂—CH(—OH)—CH₂—N⁺(CH₂—CH₂—OH)₃•X⁻, —CH₂—CH(—OH)—CH₂—N⁺(Z—CH₃)₃•X⁻,—CH₂—CH(—OH)—CH₂— N⁺(Z—CH₃)₃•X⁻, —CH₂—COO⁻•Na⁺, —CH₂—COO⁻•Na⁺, or saltsthereof; or salts thereof; —CH₂—N(—CH₃)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃,—C(═O)—CH₂—CH₂—COOH, —C(═O)—CH₂—CH₂—COOH, —C(═O)—CH₂—COOH,—C(═O)—CH₂—COOH, —SO₃H, —SO₃H, —PO₃H₂, —PO₃H₂, —CH₂—N[CH₂—N⁺(CH₃)₃•X⁻]₂,—CH₂—N[CH₂—N⁺(CH₃)₃•X⁻]₂, —CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃•X⁻,—CH₂—CH(—OH)—CH₂— N⁺(CH₃)₃•X⁻, —CH₂—CH(—OH)—CH₂—N[Z—CH₃]₂, or—CH₂—CH(—OH)—CH₂—N[Z—CH₃]₂ or —CH₂—CH(—OH)—CH₂—NH—CH₂—CH₂—OH—CH₂—N(—CH₃)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃, —C(═O)—CH₂—CH₂—COOH,—C(═O)—CH₂—CH₂—COOH, —C(═O)—CH₂—COOH, —C(═O)—CH₂—COOH, —SO₃H, —SO₃H,—PO₃H₂, —PO₃H₂, —CH₂—N[CH₂—N⁺(CH₃)₃•Br⁻]₂, —CH₂—N[CH₂—N⁺(CH₃)₃•Br⁻]₂,—CH₂—CH(—OH)—CH₂— N⁺(CH₃)₃•Cl⁻, —CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃•Cl⁻, or—CH₂—CH(—OH)—CH₂—N[Z—CH₃]₂. or —CH₂—CH(—OH)—CH₂—N[Z—CH₃]₂.—CH₂—N(—CH₃)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃, —C(═O)—CH₂—CH₂—COOH,—C(═O)—CH₂—CH₂—COOH, or —C(═O)—CH₂—COOH or —C(═O)—CH₂—COOH—CH₂—N[CH₂—N⁺(CH₃)₃•X⁻]₂ —CH₂—N[CH₂—N⁺(CH₃)₃•X⁻]₂ or—CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃•X⁻ or —CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃•X⁻—CH₂—COO⁻•Na⁺ —CH₂—COO⁻•Na⁺ —CH₂—COO⁻•Na⁺ —CH₂—COO⁻•Na⁺—CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃•Cl⁻ —CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃•Cl⁻—CH₂—CH(—OH)—CH₂—N—(CH₂—CH₂—OH)₂ —CH₂—CH(—OH)—CH₂—N—(CH₂—CH₂—OH)₂ R³ R⁴—CH₂—N(—CH₃)—Z—CH₃, —N(—CH₃)—Z—CH₃, —C(═O)—CH₂—CH₂—COOH,—O—C(═O)—CH₂—CH₂—COOH, —C(═O)—CH₂—COOH, —O—C(═O)—CH₂—COOH, —SO₃H,—O—SO₃H, —PO₃H₂, —O—PO₃H₂, —CH₂—N[CH₂—N⁺(CH₃)₃•X⁻]₂,—N[CH₂—N⁺(CH₃)₃•X⁻]₂, —CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃•X⁻, —N⁺H₃•X⁻,—CH₂—CH(—OH)—CH₂—N[Z—CH₃]₂, —N[Z—CH₃]₂, —CH₂—CH(—OH)—CH₂—NH—CH₂—CH₂—OH,—NH—CH₂—CH₂—OH, —CH₂—CH(—OH)—CH₂—N—(CH₂—CH₂—OH)₂, —N—(CH₂—CH₂—OH)₂,—CH₂—CH(—OH)—CH₂—N⁺(CH₂—CH₂—OH)₃•X⁻, —N⁺(CH₂—CH₂—OH)₃•X⁻,—CH₂—CH(—OH)—CH₂— N⁺(Z—CH₃)₃•X⁻, —N⁺(Z—CH₃)₃•X⁻, —CH₂—COO⁻•Na⁺, —Z—CH₃,or salts thereof; or salts thereof; —CH₂—N(—CH₃)—Z—CH₃, —N(—CH₃)—Z—CH₃,—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—CH₂—COOH, —C(═O)—CH₂—COOH,—O—C(═O)—CH₂—COOH, —SO₃H, —O—SO₃H, —PO₃H₂, —O—PO₃H₂,—CH₂—N[CH₂—N⁺(CH₃)₃•X⁻]₂, —N[CH₂—N⁺(CH₃)₃•X⁻]₂, —CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃•X⁻, —N⁺H₃•X⁻, or —CH₂—CH(—OH)—CH₂—N[Z—CH₃]₂ —N[Z—CH₃]₂, or—NH—CH₂—CH₂—OH —CH₂—N(—CH₃)—Z—CH₃, —N(—CH₃)—Z—CH₃, —C(═O)—CH₂—CH₂—COOH,—O—C(═O)—CH₂—CH₂—COOH, —C(═O)—CH₂—COOH, —O—C(═O)—CH₂—COOH, —SO₃H,—O—SO₃H, —PO₃H₂, —O—PO₃H₂, —CH₂—N[CH₂—N⁺(CH₃)₃•Br⁻]₂,—N[CH₂—N⁺(CH₃)₃•Br⁻]₂, —CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃•Cl⁻, —N⁺H₃•Br⁻, or—CH₂—CH(—OH)—CH₂—N[Z—CH₃]₂. or —N[Z—CH₃]₂. —CH₂—N(—CH₃)—Z—CH₃,—N(—CH₃)—Z—CH₃, —C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—CH₂—COOH, or—C(═O)—CH₂—COOH or —O—C(═O)—CH₂—COOH —CH₂—N[CH₂—N⁺(CH₃)₃•X⁻]₂—N(—CH₃)—Z—CH₃ or —CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃•X⁻ or —N[Z—CH₃]₂—CH₂—COO⁻•Na⁺ —N[Z—CH₃]₂ —CH₂—COO⁻•Na⁺ —Z—CH₃—CH₂—CH(—OH)—CH₂—N⁺(CH₃)₃•Cl⁻ —Z—CH₃ —CH₂—CH(—OH)—CH₂—N—(CH₂—CH₂—OH)₂—Z—CH₃ R⁵ R⁶ —N(—CH₃)—Z—CH³, —N(—CH₃)—Z—CH₃, —O—C(═O)—CH₂—CH₂—COOH,—O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH, —O—C(═O)—CH₂—COOH, —O—SO₃H,—O—SO₃H, —O—PO₃H₂, —O—PO₃H₂, —N[CH₂—N⁺(CH₃)₃•X⁻]₂, —N[CH₂—N⁺(CH₃)₃•X⁻]₂,—N⁺H₃•X⁻, —N⁺H₃•X⁻, —N[Z—CH₃]₂, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH,—NH—CH₂—CH₂—OH, —N—(CH₂—CH₂—OH)₂, —N—(CH₂—CH₂—OH)₂, —N⁺(CH₂—CH₂—OH)₃•X⁻,—N⁺(CH₂—CH₂—OH)₃•X⁻, —N⁺(Z—CH₃)₃•X⁻, —N⁺(Z—CH₃)₃•X⁻, —Z—CH₃, —Z—CH₃, orsalts thereof; or salts thereof: —N(—CH₃)—Z—CH₃, —N(—CH₃)—Z—CH₃,—O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH,—O—C(═O)—CH₂—COOH, —O—SO₃H, —O—SO₃H, —O—PO₃H₂, —O—PO₃H₂,—N[CH₂—N⁺(CH₃)₃•X⁻)₂, —N[CH₂—N⁺(CH₃)₃•X⁻]₂, —N⁺H₃•X⁻, —N⁺H₃•X⁻,—N[Z—CH₃]₂, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH, or —NH—CH₂—CH₂—OH, or—N—(CH₂—CH₂— OH)₂ —N(—CH₃)—Z—CH₃, —N(—CH₃)—Z—CH₃, —O—C(═O)—CH₂—CH₂—COOH,—O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH, —O—C(═O)—CH₂—COOH, —O—SO₃H,—O—SO₃H, —O—PO₃H₂, —O—PO₃H₂, —N[CH₂—N⁺(CH₃)₃•Br⁻]₂,—N[CH₂—N⁺(CH₃)₃•Br⁻]₂, —N⁺H₃•Br⁻, —N⁺H₃•Br⁻, or —N[Z—CH₃]₂. or—N[Z—CH₃]₂. —N(—CH₃)—Z—CH₃, —N(—CH₃)—Z—CH₃, —O—C(═O)—CH₂—CH₂—COOH,—O—C(═O)—CH₂—CH₂—COOH, or —O—C(═O)—CH₂—COOH or —O—C(═O)—CH₂—COOH—N(—CH₃)—Z—CH₃ —N(—CH₃)—Z—CH₃ or —N[Z—CH₃]₂ or —N[Z—CH₃]₂ —N[Z—CH₃]₂—N[Z—CH₃]₂ —Z—CH₃ —Z—CH₃ —Z—CH₃ —Z—CH₃ —Z—CH₃ —Z—CH₃

Examples of compounds represented by formula III include, but are notlimited to, the following compounds:

In some embodiments, a compound is of formula IV:

-   -   wherein R⁷ may be —N(—CH₃)—Z—CH₃, —N[CH₂—N⁺(CH₃)₃X⁻]₂,        —N⁺(CH₃)₃.X⁻, —N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH,        —N—(CH₂—CH₂—OH)₂, —N⁺(CH₂—CH₂—OH)₃.X⁻, —N—(CH₂—CH₂—COOH)₂, or        salts thereof. In some embodiments, R⁷ may be —N(—CH₃)—Z—CH₃,        —N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺(CH₃)₃.X⁻, —N⁺H₃.X⁻, —N[Z—CH₃]₂,        —NH—CH₂—CH₂—OH, or —N—(CH₂—CH₂—OH)₂. In some embodiments, R⁷ may        be —N(—CH₃)—Z—CH₃, —N[CH₂—N⁺(CH₃)₃X⁻]₂, —N⁺(CH₃)₃.X⁻, or        —N⁺H₃.X⁻, —N[Z—CH₃]₂.

In some embodiments, R⁸ may be —OH, —O—C(═O)—Z—CH₃, —N(—CH₃)—Z—CH₃,—O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH, —N[CH₂—N⁺(CH₃)₃.X⁻]₂,—N⁺H₃.X⁻, —N[Z—CH₃]₂, —N⁺(Z—CH₃)₃.X⁻, —NH—CH₂—CH₂—OH, —N—(Ch₂—CH ₂—OH)₂,—N⁺(CH₂—CH₂OH)₃.X⁻, —O—Z—CH₃, or salts thereof. In some embodiments, R⁸may be —OH, —O—C(═O)—Z—CH₃, —N(—CH₃)—Z—CH₃, —O—C(═O)—CH₂—CH₂—COOH,—O—C(═O)—CH₂—COOH, —N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂,—N⁺(Z—CH₃)₃.X⁻, —NH—CH₂—CH₂—OH, or —N—(CH₂—CH₂—OH)₂. In some embodimentsR⁸ may be —OH, —O—C(═O)—Z—CH₃, —N(—CH₃)—Z—CH₃, —O—C(═O)—CH₂—CH₂—COOH,—O—C(═O)—CH₂—COOH, —N[CH₂—N⁺(CH₃)₃.X⁻]₂, or —N⁺H₃.X⁻.

In some embodiments, R⁹ may be —H, —CH₂—O—C(═O)—Z—CH₃,—CH₂—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,—CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, —CH₂—N—(CH₂—CH₂—OH)₂,—CH₂—N⁺(CH₂—CH₂—OH)₃, —CH₂—O—Z—CH₃, —CH₂—N⁺(Z—CH₃)₃.X⁻, or saltsthereof. In some embodiments, R⁹ may be —H, —CH₂—O—C(═O)—Z—CH₃,—CH₂—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,—CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, —CH₂—N—(CH₂—CH₂—OH)₂, or—CH₂—N⁺(CH₂—CH₂—OH)₃. In some embodiments, R⁹ may be —H,—CH₂—O—C(═O)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—CH₂—CH₂—COOH,—CH₂—O—C(═O)—CH₂—COOH, —CH₂—N[Z—CH₃]₂, or —CH₂—NH—CH₂—CH₂—OH.

In some embodiments, R¹⁰ may be —H, —CH₂—O—C(═O)—Z—CH₃,—CH₂—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,—CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, —CH₂—N—(CH₂—CH₂—OH)₂,—CH₂—N⁺(CH₂—CH₂—OH)₃, —CH₂—O—Z—CH₃, —CH₂—N⁺(Z—CH₃)₃.X⁻, or saltsthereof. In some embodiments, R¹⁰ may be —H, —CH₂—O—C(═O)—Z—CH₃,—CH₂—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,—CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, or —CH₂—N—(CH₂—CH₂—OH)₂. In someembodiments, R¹⁰ may be —H, —CH₂—O—C(═O)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃,—CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH, or —CH₂—N[Z—CH₃]₂.

In some embodiments, R¹¹ may be —H, —CH₂—O—C(═O)—Z—CH₃,—CH₂—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,—CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, —CH₂—N—(CH₂—CH₂—OH)₂,—CH₂—N⁺(CH₂—CH₂—OH)₃, —CH₂—O—Z—CH₃, —CH₂—N⁺(Z—CH₃)₃.X⁻, or saltsthereof. In some embodiments, R¹¹ may be —H, —CH₂—O—C(═O)—Z—CH₃,—CH₂—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,—CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, —CH₂—N—(CH₂—CH₂—OH)₂, or—CH₂—N⁺(CH₂—CH₂—OH)₃. In some embodiments, R¹¹ may be —H,—CH₂—O—C(═O)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—CH₂—CH₂—COOH,—CH₂—O—C(═O)—CH₂—COOH, —CH₂—N[Z—CH₃]₂, or —CH₂—NH—CH₂—CH₂—OH.

In some embodiments, R¹² may be —H, —CH₂—O—C(═O)—Z—CH₃,—CH₂—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,—CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, —CH₂—N—(CH₂—CH₂—OH)₂,—CH₂—N⁺(CH₂—CH₂—OH)₃, —CH₂—O—Z—CH₃, —CH₂—N⁺(Z—CH₃)₃.X⁻, or saltsthereof. In some embodiments, R¹² may be —H, —CH₂—O—C(═O)—Z—CH₃,—CH₂—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,—CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, —CH₂—N—(CH₂—CH₂—OH)₂, or—CH₂—N⁺(CH₂—CH₂—OH)₃. In some embodiments, R¹² may be —H,—CH₂—O—C(═O)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—CH₂—CH₂—COOH,—CH₂—O—C(═O)—CH₂—COOH, —CH₂—N[Z—CH₃]₂, or —CH₂—NH—CH₂—CH₂—OH.

In some embodiments, R¹³ may be —OH, —O—C(═O)—Z—CH₃, —N(—CH₃)—Z—CH₃,—O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH, —N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N³⁰H₃.X⁻, —N[Z—CH₃]₂, —N⁺(Z—CH₃)₃.X⁻, —NH—CH₂—CH₂—OH, —N—(CH₂—CH₂—OH)₂,—N⁺(CH₂—CH₂—OH)₃.X⁻, —O—Z—CH₃, or salts thereof. In some embodiments,R¹³ may be —OH, —O—C(═O)—Z—CH₃, —N(—CH₃)—Z—CH₃, —O—C(═O)—CH₂—CH₂—COOH,—O—C(═O)—CH₂—COOH, —N[CH₂—N⁺CH₃)₃.X⁻]₂, —N³⁰ N₃.X⁻, —N[Z—CH₃]₂,—N⁺(Z—CH₃)₃.X⁻, —NH—CH₂—CH₂—OH, or —N—(CH₂—CH₂—OH)₂. In someembodiments, R¹³ may be —OH, —O—C(═O)—Z—CH₃, —N(—CH₃)—Z—CH₃,—O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—COOH, —N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N³⁰H₃.X⁻, or —N[Z—CH₃]₂.

In some embodiments, R¹⁴ may be —N(—CH₃)—Z—CH₃, —N[CH₂—N⁺(CH₃)₃.X⁻]₂,—N³⁰ (CH₃)₃.X⁻, —N³⁰H₃.X^(−, —N[Z—CH) ₃]₂, —NH—CH₂—CH₂—OH,—N—(CH₂—CH₂—OH)₂, —N⁺(CH₂—CH₂—OH)₃.X⁻, —N—(CH₂—CH₂—COOH)₂, or saltsthereof. In some embodiments, R¹⁴ may be —N(—CH₃)—Z—CH₃,—N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N³⁰ (CH₃)₃.X⁻, —N⁺H₃.X⁻, —N[Z—CH₃]₂,—NH—CH₂—CH₂—OH, or —N—(CH₂—CH₂—OH)₂. In some embodiments. R¹⁴ may be—N(—CH₃)—Z—CH₃, —N[CH₂—N⁺(CH₃)₃.X⁻]₂, —N⁺(CH₃)₃.X⁻, or —N⁺H₃.X⁻,—N[Z—CH₃]₂.

In some embodiments, E may be —CH₂—, —C(CH₃)₂—, —S—, —S(═O)₂—, —S(═O)—,—CH(CCl₃)—, —C(Cl)₂—, —O—, or —C(F)₂—.

In some embodiments, each Z may be, independently, independently, C₁-C₂₅alkylene, C₁-C₂₅ substituted alkylene, C₆-C₂₅ arylene, C₆-C₂₅substituted arylene, C₁-C₂₅ alkenylene, C₂-C₂₅ substituted alkenylene,C₂-C₂₅ alkynylene, C₂-C₂₅ substituted alkynylene, or absent.

In some embodiments, X may be Cl, Br, F, I, or OH.

In some embodiments, in compound of formula IV, at least one of R⁷, R⁸,R⁹, R¹⁰, R¹¹, R¹², R¹³, and R¹⁴ is hydrophobic, and at least one of R⁷,R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, and R¹⁴ is hydrophobic.

In some embodiments, the compound of formula IV may have substitutionsat each of independently, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, and R¹⁴ asshown in Table 4:

TABLE 4 E R⁷ R⁸ R⁹ —CH₂—, —N(—CH₃)—Z—CH₃, —OH, —H, —C(CH₃)₂—,—N[CH₂—N⁺(CH₃)₃X⁻]₂, —O—C(═O)—Z—CH₃, —CH₂—O—C(═O)—Z—CH₃, —S—,—N⁺(CH₃)₃•X⁻, —N(—CH₃)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃, —S(═O)₂—, —N⁺H₃•X⁻,—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—CH₂—COOH, —S(═O)—, —N[Z—CH₃]₂,—O—C(═O)—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH, —CH(CCl₃)—, —NH—CH₂—CH₂—OH,—N[CH₂—N⁺(CH₃)₃•X⁻]₂, —CH₂—N[Z—CH₃]₂, —C(Cl)₂—, —N—(CH₂—CH₂—OH)₂,—N⁺H₃•X⁻, —CH₂—NH—CH₂—CH₂—OH, —O—, or —N⁺(CH₂—CH₂—OH)₃•X⁻, —N[Z—CH₃]₂,—CH₂—N—(CH₂—CH₂—OH)₂, —C(F)₂—. —N—(CH₂—CH₂—COOH)₂, —N⁺(Z—CH₃)₃•X⁻,—CH₂—N⁺(CH₂—CH₂—OH)₃, or salts —NH—CH₂—CH₂—OH, —CH₂—O—Z—CH₃, thereof;—N—(CH₂—CH₂—OH)₂, —CH₂—N⁺(Z—CH₃)₃•X⁻, —N⁺(CH₂—CH₂—OH)₃•X⁻, or salts—O—Z—CH₃, thereof or salts thereof —CH₂—, —N(—CH₃)—Z—CH₃, —OH, —H,—C(CH₃)₂—, —N[CH₂—N⁺(CH₃)₃X⁻]₂, —O—C(═O)—Z—CH₃, —CH₂—O—C(═O)—Z—CH₃, —S—,—N⁺(CH₃)₃•X⁻, —N(—CH₃)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃, —S(═O)₂—, —N⁺H₃•X⁻,—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—CH₂—COOH, —S(═O)—, —N[Z—CH₃]₂,—O—C(═O)—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH, —CH(CCl₃)—, —NH—CH₂—CH₂—OH,—N[CH₂—N⁺(CH₃)₃•X⁻]₂, —N⁺H₃•X⁻, —CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH,—C(Cl)₂—, or —N[Z—CH₃]₂, or —O—, or —N—(CH₂—CH₂—OH)₂ —N⁺(Z—CH₃)₃•X⁻,—CH₂—N—(CH₂—CH₂—OH)₂ —C(F)₂—. or —NH—CH₂—CH₂—OH —C—(CH₃)₂ —N⁺(CH₃)₃•Cl⁻—OH —CH₂—N⁺(Z—CH₃)₃•Cl⁻ —C—(CH₃)₂ —N(CH₂—CH₂—OH)₂ —OH—CH₂—N⁺(Z—CH₃)₃•Cl⁻ —C—(CH₃)₂ —N(CH₂—CH₂—COO⁻•Na⁺)₂ —OH—CH₂—N⁺(Z—CH₃)₃•X⁻ —C—(CH₃)₂ —N⁺(CH₃)₃•Cl⁻ —O—C(═O)—Z—CH₃ —H —C—(CH₃)₂—N(CH₂—CH₂—OH)₂ —N⁺(Z—CH₃)₃•X⁻ —H —C—(CH₃)₂ —N(CH₂—CH₂—COO⁻•Na⁺)₂—N⁺(Z—CH₃)₃•X⁻ —H —C—(CH₃)₂ —N(Z—CH₃)₂ —OH —CH₂—N(Z—CH₃)₂ R¹⁰ R¹¹ —H,—H, —CH₂—O—C(═O)—Z—CH₃, —CH₂—O—C(═O)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃,—CH₂—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—CH₂—CH₂—COOH,—CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,—CH₂—N[Z—CH₃]₂, —CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, —CH₂—NH—CH₂—CH₂—OH,—CH₂—N—(CH₂—CH₂—OH)₂, —CH₂—N—(CH₂—CH₂—OH)₂, —CH₂—N⁺(CH₂—CH₂—OH)₃,—CH₂—N⁺(CH₂—CH₂—OH)₃, —CH₂—O—Z—CH₃, —CH₂—O—Z—CH₃, —CH₂—N⁺(Z—CH₃)₃•X⁻,—CH₂—N⁺(Z—CH₃)₃•X⁻, or salts or salts thereof thereof —H, —H,—CH₂—O—C(═O)—Z—CH₃, —CH₂—O—C(═O)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃,—CH₂—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—CH₂—CH₂—COOH,—CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,—CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, —CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH,or or —CH₂—N—(CH₂—CH₂—OH)₂ —CH₂—N—(CH₂—CH₂—OH)₂ —H —CH₂—N⁺(Z—CH₃)₃•Cl⁻—H —CH₂—N⁺(Z—CH₃)₃•Cl⁻ —H —CH₂—N⁺(Z—CH₃)₃•X⁻ —H —H —H —H —H —H—CH₂—N—[CH₂—CH₂—OH]₂ —CH₂—N—[Z—CH₃]₂ R¹² R¹³ R¹⁴ —H, —OH,—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—Z—CH₃, —O—C(═O)—Z—CH₃, —N[CH₂—N⁺(CH₃)₃X⁻]₂,—CH₂—N(—CH₃)—Z—CH₃, —N(—CH₃)—Z—CH₃, —N⁺(CH₃)₃•X⁻,—CH₂—O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—CH₂—COOH, —N⁺H₃•X⁻,—CH₂—O—C(═O)—CH₂—COOH, —O—C(═O)—CH₂—COOH, —N[Z—CH₃]₂, —CH₂—N[Z—CH₃]₂,—N[CH₂—N⁺(CH₃)₃•X⁻]₂, —NH—CH₂—CH₂—OH, —CH₂—NH—CH₂—CH₂—OH, —N⁺H₃•X⁻,—N—(CH₂—CH₂—OH)₂, —CH₂—N—(CH₂—CH₂—OH)₂, —N[Z—CH₃]₂, —N⁺(CH₂—CH₂—OH)₃•X⁻,—CH₂—N⁺(CH₂—CH₂—OH)₃, —N⁺(Z—CH₃)₃•X⁻, —N—(CH₂—CH₂—COOH)₂, —CH₂—O—Z—CH₃,—NH—CH₂—CH₂—OH, or salts —CH₂—N⁺(Z—CH₃)₃•X⁻, —N—(CH₂—CH₂—OH)₂, thereofor salts —N⁺(CH₂—CH₂—OH)₃•X⁻, thereof —O—Z—CH₃, or salts thereof —H,—OH, —N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—Z—CH₃, —O—C(═O)—Z—CH₃,—N[CH₂—N⁺(CH₃)₃X⁻]₂, —CH₂—N(—CH₃)—Z—CH₃, —N(—CH₃)—Z—CH₃, —N⁺(CH₃)₃•X⁻,—CH₂—O—C(═O)—CH₂—CH₂—COOH, —O—C(═O)—CH₂—CH₂—COOH, —N⁺H₃•X⁻,—CH₂—O—C(═O)—CH₂—COOH, —O—C(═O)—CH₂—COOH, —N[Z—CH₃]₂, —CH₂—N[Z—CH₃]₂,—CH₂—NH—CH₂—CH₂—OH, —N[CH₂—N⁺(CH₃)₃•X⁻]₂, —N⁺H₃•X⁻, —NH—CH₂—CH₂—OH, or—N[Z—CH₃]₂, or —CH₂—N—(CH₂—CH₂—OH)₂ —N⁺(Z—CH₃)₃•X⁻, —N—(CH₂—CH₂—OH)₂—NH—CH₂—CH₂—OH, or —N—(CH₂—CH₂—OH)₂ —H —OH —N⁺(CH₃)₃•Cl⁻ —H —OH—N(CH₂—CH₂—OH)₂ —H —OH —N(CH₂—CH₂—COO⁻•Na⁺)₂ —H —O—C(═O)—Z—CH₃—N⁺(CH₃)₃•Cl⁻ —H —N⁺(Z—CH₃)₃•X⁻ —N(CH₂—CH₂—OH)₂ —H —N⁺(Z—CH₃)₃•X⁻—N(CH₂—CH₂—COO⁻•Na⁺)₂ —CH₂—N(CH₂—CH₂—OH)₂ —OH —N(CH₂—CH₂—OH)₂

Examples of compounds represented by formula IV include, but are notlimited to, the following compounds:

In some embodiments, a compound is of formula V:

-   -   wherein R¹⁵ may be —N(—CH₃)—Z—CH₃, —N[CH₂—N⁺(CH₃)₃X⁻]₂,        —N⁺(Z—CH₃)₃.X⁻, —N⁺H₃.X⁻, —N⁺(CH₃)₃.X⁻, —N[Z—CH₃]₂,        —NH—CH₂—CH₂—OH, —N—(CH₂—CH₂—OH)₂, —N⁺(CH₂—CH₂—OH)₃.X⁻,        —N—(CH₂—CH₂—COOH)₂, or salts thereof. In some embodiments, R¹⁵        may be —N(—CH₃)—Z—CH₃, —N[CH₂—N⁺(CH₃)₃X⁻]₂, —N⁺(Z—CH₃)₃.X⁻,        —N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH, or —N—(CH₂—CH₂—OH)₂. In        some embodiments, R¹⁵ may be —N(—CH₃)—Z—CH₃,        —N[CH₂—N⁺(CH₃)₃X⁻]₂, —N⁺(Z—CH₃)₃.X⁻, —N⁺H₃.X⁻, or —N[Z—CH₃]₂.

In some embodiments, R¹⁶ may be —H, —CH₂—O—C(═O)—Z—CH₃,—CH₂—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,—CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, —CH₂—N—(CH₂—CH₂—OH)₂,—CH₂—N⁺(CH₂—CH₂—OH)₃.X⁻, —CH₂—O—Z—CH₃, —CH₂—N⁺(Z—CH₃)₃.X⁻,—CH₂—N⁺(CH₃)₃.X⁻, —CH₂—O—CH₂—CHOH—CH₂—N(Z—CH₃)₂, —CH₂—N—(CH₂—CH₂—COOH)₂,or salts thereof. In some embodiments, R¹⁶ may be —H,—CH₂—O—C(═O)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—CH₂—CH₂—COOH,—CH₂—O—C(═O)—CH₂—COOH, —CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH,—CH₂—N—(CH₂—CH₂—OH)₂, —CH₂—N⁺(CH₂—CH₂—OH)₃.X⁻, or —CH₂—O—Z—CH₃. In someembodiments, R¹⁶ may be —H, —CH₂—O—C(═O)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃,—CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH, —CH₂—N[Z—CH₃]₂, or—CH₂—NH—CH₂—CH₂—OH.

In some embodiments, R¹⁷ may be —H, —CH₂—O—C(═O)—Z—CH₃,—CH₂—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,—CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, —CH₂—N—(CH₂—CH₂—OH)₂,—CH₂—N⁺(CH₂—CH₂—OH)₃.X⁻, —CH₂—O—Z—CH₃, —CH₂—N⁺(Z—CH₃)₃.X⁻,—CH₂—O—CH₂—CHOH—CH₂—N(Z—CH₃)₂, —CH₂—N—(CH₂—CH₂—COOH)₂,or salts thereof.In some embodiments, R¹⁷ may be —H, —CH₂—O—C(═O)—Z—CH₃,—CH₂—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,—CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, —CH₂—N—(CH₂—CH₂—OH)₂,—CH₂—N⁺(CH₂—CH₂—OH)₃.X⁻, —CH₂—O—Z—CH₃, or —CH₂—N⁺(Z—CH₃)₃.X⁻. In someembodiments, R¹⁷ may be —H, —CH₂—O—C(═O)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃,—CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH, —CH₂—N[Z—CH₃]₂, or—CH₂—NH—CH₂—CH₂—OH, —CH₂—N—(CH₂—CH₂—OH)₂.

In some embodiments. R¹⁸ may be —CH₂—O—C(═O)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃,—CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH, —CH₂—N[Z—CH₃]₂,—CH₂—NH—CH₂—CH₂—OH, —CH₂—N—(CH₂—CH₂—OH)₂, —CH₂—N⁺(CH₂—CH₂—OH)₃.X⁻,—CH₂—O—Z—CH₃, —CH₂—N⁺(Z—CH₃)₃.X⁻, —CH₂—O—CH₂—CHOH—CH₂—N(Z—CH₃)₂,—CH₂—N—(CH₂—CH₂—COOH)₂, or salts thereof In some embodiments, R¹⁸ may be—CH₂—O—C(═O)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—CH₂—CH₂—COOH,—CH₂—O—C(═O)—CH₂—COOH, —CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH,—CH₂—N—(CH₂—CH₂—OH)₂, —CH₂—N⁺(CH₂—CH₂—OH)₃.X⁻, —CH₂—O—Z—CH₃, or—CH₂—N⁺(Z—CH₃)₃.X⁻. In some embodiments, R¹⁸ may be —CH₂—O—C(═O)—Z—CH₃,—CH₂—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,—CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, or —CH₂—N—(CH₂—CH₂—OH)₂.

In some embodiments, each Z may be, independently, independently, C₁-C₂₅alkylene, C₁-C₂₅ substituted alkylene, C₆-C₂₅ arylene, C₆-C₂₅substituted arylene, C₂-C₂₅ alkenylene, C₂-C₂₅ substituted alkenylene,C₂-C₂₅ alkynylene, C₂-C₂₅ substituted alkynylene, or absent.

In some embodiments, X may be Cl, Br, F, I, or OH.

In some embodiments, in compound of formula V, at least one of R¹⁵, R¹⁶,R¹⁷, and R¹⁸ is hvdrophilic, and at least one of R¹⁵, R¹⁶, R¹⁷, and R¹⁸is hydrophobic.

In some embodiments, the compound of formula V may have substitutions ateach of, independently, R¹, R², R³, and R⁴ as shown in Table 5:

TABLE 5 R¹⁵ R¹⁶ R¹⁷ —N(—CH₃)—Z—CH₃, —H, —H, —N[CH₂—N⁺(CH₃)₃X⁻]₂,—CH₂—O—C(═O)—Z—CH₃, —CH₂—O—C(═O)—Z—CH₃, —N⁺(Z—CH₃)₃•X⁻,—CH₂—N(—CH₃)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃, —N⁺H₃•X⁻,—CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—CH₂—COOH, —N⁺(CH₃)₃•X⁻,—CH₂—O—C(═O)—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH, —N[Z—CH₃]₂,—CH₂—N[Z—CH₃]₂, —CH₂—N[Z—CH₃]₂, —NH—CH₂—CH₂—OH, —CH₂—NH—CH₂—CH₂—OH,—CH₂—NH—CH₂—CH₂—OH, —N—(CH₂—CH₂—OH)₂, —CH₂—N—(CH₂—CH₂—OH)₂,—CH₂—N—(CH₂—CH₂—OH)₂, —N⁺(CH₂—CH₂—OH)₃•X⁻, —CH₂—N⁺(CH₂—CH₂—OH)₃•X⁻,—CH₂—N⁺(CH₂—CH₂—OH)₃•X⁻, —N—(CH₂—CH₂—COOH)₂, —CH₂—O—Z—CH₃, —CH₂—O—Z—CH₃,or salts thereof —CH₂—N⁺(Z—CH₃)₃•X⁻, —CH₂—N⁺(Z—CH₃)₃•X⁻,—CH₂—O—CH₂—CHOH—CH₂—N(Z—CH₃)₂, —CH₂—O—CH₂—CHOH—CH₂—N(Z—CH₃)₂,—CH₂—N⁺(CH₃)₃•X⁻, —CH₂—N—(CH₃—CH₂—COOH)₂, —CH₂—N—(CH₂—CH₂—COOH)₂, orsalts thereof or salts thereof —N(—CH₃)—Z—CH₃, —H, —H,—N[CH₂—N⁺(CH₃)₃X⁻]₂, —CH₂—O—C(═O)—Z—CH₃, —CH₂—O—C(═O)—Z—CH₃,—N⁺(Z—CH₃)₃•X⁻, —CH₂—N(—CH₃)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃, —N⁺H₃•X⁻,—CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—CH₂—COOH, —N[Z—CH₃]₂,—CH₂—O—C(═O)—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH, —NH—CH₂—CH₂—OH,—CH₂—N[Z—CH₃]₂, —CH₂—N[Z—CH₃]₂, or —N—(CH₂—CH₂—OH)₂ —CH₂—NH—CH₂—CH₂—OH,—CH₂—NH—CH₂—CH₂—OH, —CH₂—N—(CH₂—CH₂—OH)₂, —CH₂—N—(CH₂—CH₂—OH)₂, or—CH₂—N⁺(CH₂—CH₂—OH)₃ or —CH₂—N⁺(CH₂—CH₂—OH)₃ —N(—CH₃)—Z—CH₃, —H, —H,—N[CH₂—N⁺(CH₃)₃X⁻]₂, —CH₂—O—C(═O)—Z—CH₃, —CH₂—O—C(═O)—Z—CH₃,—N⁺(Z—CH₃)₃•X⁻, —CH₂—N(—CH₃)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃, —N⁺H₃•X⁻,—CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—CH₂—COOH, or —N[Z—CH₃]₂ or—CH₂—O—C(═O)—CH₂—COOH —CH₂—O—C(═O)—CH₂—COOH, or —CH₂—N[Z—CH₃]₂—N⁺(CH₃)₃•Cl⁻ —CH₂—O—CH₂—CHOH—CH₂—N(Z—CH₃)₂—CH₂—O—CH₂—CHOH—CH₂—N(Z—CH₃)₂ —N⁺(CH₃)₃•Cl⁻ —CH₂—N⁺(CH₃)₃•Cl⁻—CH₂—N⁺(Z—CH₃)₃•Cl⁻ —N⁺(CH₃)₃•Cl⁻ —CH₂—N⁺(CH₃)₃•Cl⁻ —CH₂—O—C(═O)—Z—CH₃—N⁺(CH₂—CH₂—OH)₃•X⁻ —CH₂—N⁺(CH₂—CH₂—OH)₃•X⁻ —CH₂—N(Z—CH₃)₂—N—(CH₂—CH₂—OH)₂, —CH₂—N—(CH₂—CH₂—OH)₂, —CH₂—N⁺(Z—CH₃)₃•Cl⁻—N—(CH₂—CH₂—COO⁻Na⁺)₂, —CH₂—N—(CH₂—CH₂—COO⁻Na⁺)₂, —CH₂—N⁺(Z—CH₃)₃•Cl⁻—N—(CH₂—CH₂—OH)₂, —CH₂—N—(CH₂—CH₂—OH)₂, —CH₂—N[Z—CH₃]₂ R¹⁸—CH₂—O—C(═O)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—CH₂—CH₂—COOH,—CH₂—O—C(═O)—CH₂—COOH, —CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH,—CH₂—N—(CH₂—CH₂—OH)₂, —CH₂—N⁺(CH₂—CH₂—OH)₃•X⁻, —CH₂—O—Z—CH₃,—CH₂—N⁺(Z—CH₃)₃•X⁻, —CH₂—O—CH₂—CHOH—CH₂—N(Z—CH₃)₂,—CH₂—N—(CH₂—CH₂—COOH)₂, or salts thereof —CH₂—O—C(═O)—Z—CH₃,—CH₂—N(—CH₃)—Z—CH₃, —CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH,—CH₂—N[Z—CH₃]₂, —CH₂—NH—CH₂—CH₂—OH, —CH₂—N—(CH₂—CH₂—OH)₂, or—CH₂—N⁺(CH₂—CH₂—OH)₃ —CH₂—O—C(═O)—Z—CH₃, —CH₂—N(—CH₃)—Z—CH₃,—CH₂—O—C(═O)—CH₂—CH₂—COOH, —CH₂—O—C(═O)—CH₂—COOH, or —CH₂—N[Z—CH₃]₂—CH₂—O—CH₂—CHOH—CH₂—N(Z—CH₃)₂ —CH₂—N⁺(Z—CH₃)₃•Cl⁻ —CH₂—O—C(═O)—Z—CH₃—CH₂—N(Z—CH₃)₂ —CH₂—N⁺(Z—CH₃)₃•Cl⁻ —CH₂—N⁺(Z—CH₃)₃•Cl⁻ —CH₂—N[Z—CH₃]₂

Examples of compowids represented by formula V include, but are notlimited to, the following compounds:

In some embodiments, the compounds represented by formulae I-V may begemini surfactants. These gemini surfactants may be made morehydrophobic or more hydrophilic depending on the use. For example,increasing the nonpolar chain length of the hydrophobic uoups mayincrease both the lipophilicity and surface activity, with a decrease inthe critical micellar concentration. In some embodiments, the ratio ofhydrophobic groups to hydrophilic groups may vary in the geminisurfactants described herein.

In some embodiments, the hydrophobic groups of the gemini surfactantsmay be an alkyl ether chain, an arylalkyl ether chain, an alkylesterchain, or an arylalkylester chain, with suitable chain length. Suchchains can act as anchors and prevent leachina of the surfactants whenincorporated in paints. In some embodiments, the hydrophilic groups maybe monoethanol amine, diethanol amine, or triethanol amine; anionicgroups, such as carboxylate, sulphate, sulphonate, monohydrogenphosphate, or dihydrogen phosphate, or salts of Na⁺, K⁺, Ca²⁺, Mg²⁺, orNa₄ ⁺, or any combination thereof; cationic groups, such as quaternaryammonium salts, phosphonium salts, acrylate salts, or any combinationthereof.

In some embodiments, a hydrophilic coating may include one or more ofthe gemini surfactants of formulae I-V, as described herein. Thehydrophilic coating may provide hydrophilic and/or self-cleaningproperties when applied on a substrate. As water evaporates, binderparticles pack against each other forming an irreversible networkedstructure. During this process, coalescing agents along with geminisurfactants may migrate to the surface. The gemini surfactant mayprovide a by surface to the coating, thus aiding in self-cleaning of thesurface. These surfaces are able to interact and retain water moleculesfor relatively longer periods of time, thus keeping the surface wet andhelping water to sheathe off and remove dirt. In addition, the geminisurfactants may provide anti-bacterial and anti-microbial properties tothe coating.

The hydrophilic coating described herein may be used as a decorativecoating, an industrial coating, a protective coating, a UV-protectivecoating, a self-cleaning coating, a biocidal coating, or any combinationthereof The coatings may generally be applied to any substrate. Thesubstrate may be an article, an object, a vehicle or a structure.Although no particular limitation is imposed on the substrate to be usedin the present disclosure, exemplary substrates include an exterior of abuilding, vehicles, cars, trucks, bicycles, bridges, airplanes,helicopters, metal railings, fences, glasses, plastics, metals,ceramics, wood, stones, cement, fabric, paper, leather, walls, pipes,vessels, medical devices, turbines, fan blades, propellers, and thelike. The coating may be applied to a substrate by spraying, dipping,rolling, brushing, or any combination thereof.

Gemini surfactants may be present in the coating composition at about0.5 to about 5 weight percent, at about 0.5 to about 2.5 weight percent,at about 0.5 to about 2 weight percent, at about 0.5 to about 1.5 weightpercent, or at about 0.5 to about 1 weight percent. Specific examplesinclude about 0.5 weight percent, about 1 weight percent, about 1.5weight percent, about 2 weight percent, about 2.5 weight percent, about5 weight percent of the total weight, and ranges between (and includingthe endpoints of) any two of these values. Due to the highsurface-activity, a much lower concentration of the surfactants may beneeded as compared to the conventional surfactants.

Gemini surfactants may be added to the coating during emulsionpolymerization process by substituting the conventional surfactants withthe gemini surfactants described herein. In an emulsion polymerizationprocess, the surfactant is dissolved in water until the critical micelleconcentration (CMC) is reached. The interior of the micelle provides thesite necessaiy for polymerization. The polymerization process involvesheating a mixture containing water, an initiator, monomer and asurfactant with constant stirring. The initiator/surfactant mixture andmonomer are vigorously mixed to form micelles. In some embodiments, thegemini surfactants may be mixed with conventional surfactants duringthis process. Examples of conventional surfactants that may be usedinclude, but are not limited to, alkyl phenol ethoxylates, sodium laurylsulfate, dodecylbenzenesulfonate, polyoxyethylene alkyl ethers,polyoxyethylene alkyl allyl ethers, ethylene glycols, polyoxyethylene,stearic acid and polyoxypropylene. In some embodiments, the geminisurfactants may be incorporated in the paint composition at the end ofthe process, and mixed with the paint before use. For example, an endconsumer may add the gemini surfactant to any conventional paintformulation before use.

In some embodiments, the gemini surfactants in the paint composition mayexist as molecules cross-linked to each other. The presence ofcross-linking groups, such as acrylene or styrylene groups may beinvolved in this cross-linking. In some embodiments, the geminisurfactants may exist as free molecules without cross-links. Inaddition, the gemini surfactants may also exist as cross-linked to thebinder component. The binder may be an acrylate, styrenic or a vinylpolymer. Suitable binder polymers may be polymers of alkylacrylate,alkyl methacrylate, allyl methacrylate, acrylic acid, methacrylic acid,acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate,thioethyl methacrylate, vinyl methacrylate, vinyl benzene,2-hydroxyethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate,vinyltrimethoxysilane, vinyltriethoxysilane, vinyl formate, vinylacetate, vinyl propionate, vinyl butyrate, vinyl hexanoate,vinyltoluene, α-methyl styrene, chlorostyrene, or styrenesulfonic acid,or a copolymer of any of the foregoing, or any combination thereof.

In addition, the gemini surfactants described herein may function asefficient emulsifiers and coalescing agents in paints. The geminisurfactants may self-crosslink or cross-link with the binder and mayreduce minimum film forming temperature (MFT). These gemini surfactantsmay function as non-leachable emulsifying agents due to anchoring of thehydrophobic chains, in addition to the electrostatic and physical chainentanglements with polymeric binder chains. Further, these geminisurfactants may form stable emulsion systems with improved resistance tocoagulation when subjected to low temperature or high shear stress.

The gemini surfactants described herein may behave as multi-activitysurfactants: anionic, cationic, molecular and mixed activity geminisurfactants. Further, the ratio of hydrophobic/hydrophilic active groupsmay be controlled according to the required application. Furthermore,the gemini surfactants described herein may be combined with one or moreclasses of surfactants, irrespective of active groups, whetheraliphatic, aromatic or heterocyclic.

In addition to its use in paints, the gemini surfactants may also beused as a hydrophilic material, a defoamer, an emulsifier, a dispersantfor diesel fuel mixtures, a wetting aid, a leveling aid, a phasetransfer catalyst, or a demulsifying agent.

Gemini surfactants may also be used in sunscreens, skin-cleansingcompositions, dermatology and acne care products (for example, soaps,specialty soaps, liquid hand soaps, shampoos, conditioners, showergels), household products (for example, dry and liquid laundrydetergents, dish soaps, dishwasher detergents, toilet bowl cleaners,upholstery cleaners, glass cleaners, general purpose cleaners, or fabricsofteners), hard surface cleaners (for example, floor cleaners, metalcleaners, automobile and other vehicle cleaners), pet care products (forexample, shampoos), and cleaning products in general. Other uses forgemini surfactants may be found in industrial applications inlubricants, emulsion polymerization, textile processing, miningflocculates, petroleum recovery, dispersants for pigments, wetting orleveling agents in paints and printing inks, wetting agents forhousehold and agricultural pesticides, wastewater treatment andcollection systems, off-line and continuous cleaning, and manufacture ofcross-flow membrane filters, such as reverse osmosis (RO), ultrafiltration (UF), micro filtration (MF) and nano filtration (UF), plusmembrane bioreactors (MBRs), and all types of flow-through filtersincluding multi-media filters, and many other products and processes.Further, the gemini surfactants may also be used as dispersants fortramp oil in cooling towers and after oil spills.

Preparation of Gemini Surfactants of Formula I

In some embodiments, a method of making a gemini surfactant of formula Imay include contacting any one of urea, biuret, or alkylene diamine withformaldehyde to form a hydroxymethyl compound; and contacting thehydroxymethyl compound with a dimethyl alkyl amine to form the geminisurfactant of formula I. In some embodiments, the alkyl group in thedimethyl alkyl amine may be C₁-C₂₅ carbon atoms long. In someembodiments, the urea, biuret, or alkylene diamine may be contacted withformaldehyde in a molar ratio from about 1:2 to about 1:6, from about1:2 about 1:5, from about 1:2 to about 1:4, or from about 1:2 to about1:3. Specific examples include, but are not limited to, about 1:2, about1:3, about 1:4, about 1:5, about 1:6, and ranges between any two ofthese values. The alkylene diamine may be C₁-C₁₀ alkylene diamine,particularly ethylene diamine. This process may be conducted in thepresence of a basic catalyst. Specific examples of the basic catalystinclude alkali metal hydroxides, such as KOH, LiOH, NaOH, and the like.Contacting any one of urea, biuret, or alkylene diamine with theformaldehyde and the basic catalyst may be performed in a solution.During this process, the pH of the solution may be maintained from aboutpH 8 to about pH 11, from about pH 8 to about pH 10.5, from about pH 8to about pH 10, from about 8 to about pH 9, or from about pH 8 to aboutpH 8.5. Specific examples include, but are not limited to, about pH 8,about pH 8.5, about pH 9, about pH 9.5, about pH 10, about pH 11, andranges between any two of these values (including their endpoints).

When contacting any one of urea, biuret, or alkylene diamine with theformaldehyde and the basic catalyst, the mixture may be heated to atemperatur of about 50° C. to about 90° C., about 50° C. to about 75°C., about 50° C. to about 70° C., or about 50° C. to about 60° C.Specific examples also include, but are not limited to, about 50° C.,about 65° C., about 70° C., about 80° C., about 85° C., about 90° C.,and ranges between (and including the endpoints of) any two of thesevalues. The heating may he performed for about 2 hours to about 6 hours,about 2 hours to about 5 hours, about 2 hours to about 4 hours, or about2 hours to about 3 hours. Specific ex pies include, but are not limitedto, about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6hours, and ranges between (and including the endpoints of) any two ofthese values.

In some embodiments, when contacting the hydroxymethyl compound with thedimethyl alkyl amine, the mixture may be heated to a temperature f about20° C. to about 40° C., about 20° C. to about 35° C., about 20° C. toabout 30° C., or about 20° C. to about 25° C. Specific examples alsoinclude, but are not limited to, about 20° C., about 25° C., about 30°C., about 35° C., about 40° C., and ranges between (and including theendpoints of) any two of these values. The heating may be performed forabout 2 hours to about 6 hours, about 2 hours to about 5 hours, about 2hours to about 4 hours, or about 2 hours to about 3 hours. Specificexamples include, but are not limited to, about 2 hours, about 3 hours,about 4 hours, about 5 hours, about 6 hours, and ranges between (andincluding the endpoints of) any two of these values. In someembodiments, the hydroxymethyl compound may be a di(hydroxymethyl)compound, a tri(hydroxymethyl) compound, a tetra(hydroxymethyl)compound, a poly(hydroxymethyl) compound, or any combination thereof.

Preparation of Gemini Surfactants of Formula II

In some embodiments, gemini surfactants of formula II may he prepared bycontacting melamine with formaldehyde to form a hydroxymethyl melaminederivative; contacting the hydroxymethyl melamine derivative withdiethanolamine to form a diethanol melamine derivative; and contactingthe diethanol melamine derivative with an alkyl halide.

In some embodiments, while contacting melamine with formaldehyde, themixture may be heated to a temperature of about 50° C. to about 90° C.about 50° C. to about 75° C., about 50° C. to about 70° C., or about 50°C. to about 60° C. Specific examples also include, but are not limitedto, about 50° C., about 65° C., about 70° C., about 80° C., about 85°C., about 90° C., and ranges between (and including the endpoints of)any two of these values. The heating may be performed for about 2 hoursto about 6 hours, about 2 hours to about 5 hours, about 2 hours to about4 hours, or about 2 hours to about 3 hours. Specific examples include,but are not limited to, about 2 hours, about 3 hours, about 4 hours,about 5 hours, about 6 hours, and ranges between (and including theendpoints of) any two of these values.

In some embodiments, the hydroxymethyl melamine derivative is furtherreacted with diethanol amine, and the n xture may be heated to atemperatur of about 20° C. to about 40° C., about 20° C. to about 35°C., about 20° C. to about 30° C., or about 20° C. to about 25° C.Specific examples also include, but are not limited to, about 20° C.,about 25° C., about 30° C., about 35° C., about 40° C., and rangesbetween (and including the endpoints of) any two of these values. Theheating may be performed for about 2 hours to about 6 hours. about 2hours to about 5 hours, about 2. hours to about 4 hours, or about 2hours to about 3 hours. Specific examples include, but are not limitedto, about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6hours, and ranges between (and including the endpoints of) any two ofthese values. In some embodiments, the hydroxymethyl melamine derivativemay be a tri(hydroxymethyl)melamine derivative, a tetra(hydroxymethyl)melamine derivative, a penta(hydroxymethyl) melamine derivative, a.hexa(hydroxymethyl) melamine derivative, or any combination thereof.

The melamine with diethanol amine functional groups may be furtherreacted with an alkyl halide, and the reaction may be heated to atemperature of about 30° C. to about 60° C., about 30° C. to about 55°C., about 30° C. to about 50° C., or about 30° C. to about 40° C.Specific examples also include, but are not limited to, about 30° C.,about 35° C., about 40° C., about 55° C., about 60° C., and rangesbetween (and including the endpoints of) any two of these values. Theheating may be performed for about 2 hours to about 6 hours, about 2hours to about 5 hours, about 2 hours to about 4 hours, or about 2 hoursto about 3 hours. Specific examples include, but are not limited to,about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6hours, and ranges between (and including the endpoints of) any two ofthese values. In some embodiments, the alkyl chloride may be C₁-C₂₅carbon atoms in length.

In some embodiments, gemini surfactants of formula II may be prepared bycontacting melamine with formaldehyde to form a hydroxymethyl melaminederivative; and contacting the hydroxymethyl melamine derivative withone of the following: an equimolar mixture of saturated fattyacid/oxalic acid, an equimolar mixture of saturated fattyacid/chlorosulfonic acid or an equimolar mixture of saturated fattyacid/chlorophosphonic acid.

In some embodiments, while contacting the hydroxymethyl melaminederivative with an equimolar mixture of saturated fatty acid/oxalicacid, an equimolar mixture of saturated fatty acid/chlorosulfonic acidor an equimolar mixture of saturated fatty acid/chlorophosphonic acid,the reaction mixture may be heated to a temperature of about 30° C.; toabout 80° C., about 30° C. to about 75° C., about 30° C.; to about 60°C., or about 30° C. to about 40° C. Specific examples also include, butare ot limited to, about 30° C., about 55° C., about 60° C., about 75°C., about 80° C., and ranges between (and including the endpoints of)any two of these values. The heating may be performed for about 2 hoursto about 6 hours, about 2 hours to about 5 hours, about 2 hours to about4 hours, or about 2 hours to about 3 hours. Specific examples include,but are not limited to, about 2 hours, about 3 hours, about 4 hours,about 5 hours, about 6 hours, and ranges between (and including theendpoints of) any two of these values.

In some embodiments, gemini surfactants of formula II may he prepared bycontacting melamine with formaldehyde to form a hydroxymethyl melaminederivative; and contacting the hydroxymethyl melamine derivative with adimethyl alkylamine.

In some embodiments, the hydroxymethyl melamine derivative may bereacted dimethyl amine, and the mixture may be heated to a temperatureof about 20° C. to about 40° C., about 20° C. to about 35° C., about 20°C. to about 30° C., or about 20° C. to about 25° C. Specific examplesalso include, but are not limited to, about 20° C., about 25° C., about30° C., about 35° C., about 40° C., and ranges between (and includingthe endpoints of) any two of these values. The heating may be performedfor about 2 hours to about 6 hours, about 2 hours to about 5 hours,about 2 hours to about 4 hours, or about 2hours to about 3 hours.Specific examples include, but are not limited to, about 2 hours, about3 hours, about 4 hours, about 5 hours, about 6 hours, and ranges between(and including the endpoints of) any two of these values.

Preparation of Gentini Surfactants of Formula III

In some embodiments, gemini surfactants of formula III may be preparedby contacting novolac with epichlorohydrin to form anovolac-chlorohydrin derivative; contacting the novolac-chlorohydrinderivative with diethanolamine or triethylamine to form a novolacderivative; and contacting the novolac derivative with an alkylchloride.

In some embodiments, the novolac and epichlorohydrin mixture may beheated to a temperature of about 50° C. to about 90° C., about 50° C. toabout 75° C., about 50° C. to about 70° C., or about 50 ⁰C to about 60°C. Examples also include about 50° C., about 65° C., about 70° C., about80° C., about 85° C., about 90° C., and ranges between (and includingthe endpoints of any two of these values. The heating may be performedfor a variety of times, such as about 2 hours to about 6 hours, forabout 2 hours to about 5 hours, for about 2 hours to about 4 hours, orfor about 2 hours to about 3 hours, Examples also include about 2 hours,about 3 hours, about 4 hours, about 5 hours, about 6 hours, and rangesbetween (an including the endpoints of) any two of these values.

In some embodiments, the novolac-chlorohydrin derivative may be reactedwith either diethanol amine or triethyl amine to form a. novolacderivative. The reaction may be performed at a temperature of about 50°C. to about 90° C., about 50° C. to about 75° C., about 50° C. to about70° C., or about 50° C. to about 60° C., Examples also include about 50°C., about 65° C., about 70° C., about 80° C., about 85° C., about 90°C., and ranges between (and including the endpoints of) any two of thesevalues, The heating may be performed for a variety of times, such asabout 1 hour to about 3 hours, for about 1 hours to about 2 hours, orfor about 1 hour to about 1.5 hours. Examples also include about 1 hour,about 1.5 hours, about 2 hours, about 3 hours, and ranges between (anincluding the endpoints of) any two of these values.

In some embodiments the novolac derivative may be reacted with an alkylchloride, and the alkylation may be performed by any alkylation processknown in the art. For example, the alkylation may be performed in thepresence of a Friedel-Crafts catalyst, such as AlCl₃. The alkyl halidemay be any C₁-C₂₅ carbon atom alkyl halide.

Preparation of Gemini Surfactants of Formula IV

In some embodiments, the gemini surfactants of formula IV may beprepared by contacting a bisphenol compound with epichlorohydrin andformaldehyde to form a tetramethylol bisphenol derivative; contactingthe tetramethylol bisphenol derivative with any one of the following: anequimolar mixture of trimethylamine and N,N,N,-trialkyl amine, anequimolar mixture of diethanol amine and N,N,N,-trialkyl amine, and anequimolar mixture of disodium propionate amine and N,N,N,-trialkylamine.

In some embodiments, a bisphenol compound may be contacted withepichlorohydrin and formaldehyde to form a tetramethylol bisphenolderivative. Non-limiting examples of bisphenol compound includebisphenol A, bisphenol F, bisphenol S, bisphenol sulphone, bisphenolsulphoxide, bisphenol chloral, bisphenolvinylidene dichloride, andbisphenol methylenedifluoride.

In some embodiments, the tetramethylol bisphenol derivative may bereacted with an equimolar mixture of trimethylamine and N,N,N,-trialkylamine, and the reaction may be performed at temperatures of about 30°C., to about 60° C., about 30° C. to about 55° C., about 30° C. to about50° C., or about 30° C. to about 40° C. Specific examples also include,but are not limited to, about 30° C., about 45° C., about 50° C., about55° C., about 60° C., and ranges between (and including the endpointsof) any two of these values. The heating may be performed for about 1hour to about 6 hours, about 1 hour to about 5 hours, about 1 hour toabout 4 hours, or about 1 hour to about 3 hours. Specific examplesinclude, but are not limited to, about 1 hour, about 3 hours, about 4hours, about 5 hours, about 6 hours, and ranges between (and includingthe endpoints of) any two of these values.

In some embodiments, the tetramethylol bisphenol derivative may bereacted with equimolar mixture of diethanol amine and N,N,N,-trialkylamine, and the reaction may be performed at temperatures of about 30° C.to about 60° C., about 30° C. to about 55° C., about 30° C. to about 50°C., or about 30° to about 40° C. Specific examples also include, but arenot limited to, about 30° C., about 45° C., about 50° C., about 55° C.,about 60° C., and ranges between (and including the endpoints of) anytwo of these values. The heating may be performed for about 1 hour toabout 6 hours, about 1 hour to about 5 hours, about 1 hour to about 4hours, or about 1 hour to about 3 hours. Specific examples include, butare not limited to, about 1 hour, about 3 hours, about 4 hours, about 5hours, about 6 hours, and ranges between (and including the endpointsof) any two of these values.

In some embodiments, the tetramethylol bisphenol derivative may bereacted with an equimolar mixture of disodium propionate amine andN,N,N,-trialkyl amine, and the reaction may be performed at temperaturesof about 30° C. to about 60° C., about 30° C. to about 55° C., about 30°C. to about 50° C., or about 30° C. to about 40° C. Specific examplesalso include, but are not limited to, about 30° C., about 45° C., about50° C., about 55° C., about 60° C., and ranges between (and includingthe endpoints of) any two of these values. The heating may be performedfor about 1 hour to about 6 hours; about 1 hour to about 5 hours; about1 hour to about 4 hours; or about 1 hour to about 3 hours. Specificexamples include, but are not limited to, about 1 hour, about 3 hours,about 4 hours; about 5 hours, about 6 hours, and ranges between (andincluding the endpoints of) any two of these values.

Preparation of Gemini Surfactants of Formula V

In some embodiments, the aernini surfactants of formula V may beprepared by reacting a resol with epichlorohydrin to form aresol-chlorohydrin derivation; and contacting the resol-chlorohydrinderivative y one of the following: an equimolar mixture of triethylamineand N,N,N,-trialkyl amine, an equimolar mixture of diethanol amine andN,N,N,-trialkyl amine, an equimolar mixture of disodium propionate amineand N,N,N,-trialkyl amine.

In some embodiments, while contacting resol and epichlorohydrin, themixture may be heated to a temperature of about 50° C.; to about 90° C.,about 50° C.; to about 75° C., about 50° C. to about 70° C., or about50° C. to about 60° C. Examples also include about 50° C., about 65° C.,about 70° C. about 80° C., about 85° C., about 90° C., and rangesbetween (and including the endpoints of) any two of these values. Theheating may be performed for a variety of times, such as about 2 hoursto about 6 hours, for about 2 hours to about 5 hours, for about 2 hoursto about 4 hours, or for about 2 hours to about 3 hours. Examples alsoinclude about 2 hours, about 3 hours, about 4 hours, about 5 hours,about 6 hours, and ranges between (an including the endpoints of) anytwo of these values.

In some embodiments, the resol-chlorohydrin derivative may be reactedwith an equimolar mixture of triethylamine and N,N,N,-trialkyl amine,and the reaction may be performed at temperatures of about 30° C. toabout 60° C., about 30° C. to about 55° C., about 30° C. to about 50°C., or about 30° C. to about 40° C. Specific examples also include, butare not d to, about 30° C., about 45° C., about 50° C., about 55° C.,about 60° C., and ranges between (and including the endpoints of) anytwo of these values. The heating may be performed for about 1 hour toabout 6 hours, about 1 hour to about 5 hours, about 1 hour to about 4hours, or about 1 hour to about 3 hours. Specific examples include, butare not limited to, about 1 hour, about 3 hours, about 4 hours, about 5hours, about 6 hours, and ranges between (and including the endpointsof) any two of these values.

In some embodiments, the resol-chlorohydrin derivative may be reactedwith an equimolar mixture of diethanol amine and N,N,N,-trialkyl amine,and the reaction may be performed at temperatures of about 30° C. toabout 60° C., about 30° C. to about 55° C., about 30° C. to about 50°C., or about 30° C. to about 40° C. Specific examples also include, butare not limited to, about 30° C., about 45° C., about 50° C., about 55°C., about 60° C., and ranges between (and including the endpoints of)any two of these values. The heating may be performed for about 1 hourto about 6 hours, about 1 hour to about 5 hours, about 1 hour to about 4hours, or about 1 hour to about 3 hours. Specific examples include, butare not limited to, about 1 hour, about 3 hours, about 4 hours, about 5hours, about 6 hours, and ranges between (and including the endpointsof) any two of these values,

In some embodiments, the resol-chlorohydrin derivative may be reactedwith an equimolar mixture of disodium propionate amine andN,N,N,-trialkyl amine, and the reaction may be performed at temperaturesof about 30° C., to about 60° C., about 30° C. to about 55° C., about30° C. to about 50° C., or about 30° C. to about 40° C. Specificexamples also include, but are not limited to, about 30° C., about 45°C., about 50° C., about 55° C., about 60° C., and ranges between (andincluding the endpoints ot) any two of these values. The heating may beperformed for about 1 hour to about 6 hours, about 1 hour to about 5hours, about 1 hour to about 4 hours, or about 1 hour to about 3 hours.Specific examples include, but are not limited to, about 1 hour, about 3hours, about 4 hours, about 5 hours, about 6 hours, and ranges between(and including the endpoints of) any of these values.

EXAMPLES Example 1 Preparation of Compound 2

About 60 grams of urea (1 mole) and 324 grams (4 moles) of formalinsolution (37% concentration) were mixed in a five-neck flanged topreaction flask fitted with a condenser, mechanical stirrer, droppingfunnel, and a thermometer. The reaction was started by adding 40% sodiumhydroxide solution drop wise, and the pH of the reaction mixture wasadjusted to pH 10. The reaction mixture was heated to about 65° C. for 2hours with nixing, and the pH was maintained at pH 9-pH 10. At the endof the reaction period, the reaction mixture was cooled and neutralizedwith a cold (5-10° C.) solution of sodium dihydrogen phosphate. Theproduct was desalted and dried with molecular sieves. The product wasevaporated by rotary evaporators and dried under vacuum to obtain ahydroxymethyl compound. The number of hydroxymethyl groups wasdetermined by using moisture evolution analysis technique andthermogravimetric analysis.

The above obtained hydroxymethyl compound (63.5 grams, 0.5 mole)vvasdissolved in methanol and added drop wise to two moles of N,N-dimethylheneicosylamine at 30° C. The mixture was maintained at 30° C. and mixedfor two hours, and gradually heated to 60° C. The reaction was continuedfor furthe one hour under stream of nitrogen gas. The product wasdesalted and dried with molecular sieves, The product was evaporated byrotary evaporators and dried under vacuum to obtain the cationic geminisurfactant compound 2.

Example 2 Preparation of Compound 6

A three necked reaction vessel fitted with reflux condenser,thermometer, and mechanical stirrer is charged with 126 grams ofmelamine (1 mole), and 8 moles of formalin solution (37 weight %). A 10%(weight %) sodium carbonate solution is added and the pH is maintainedbetween 8.5-9. The solution is heated to 65-70° C. for 3 hours withcontinuous mixing. At the end of this period, product is cooled to roomtemperature and excess of non-reacted formaldehyde is removed to obtainhexa-hydroxymethyl melamine.

A flanged top reaction vessel fitted with mechanical stirrer,thermometer, condenser and dropping funnel is charged with diethanolamine (107 grams, 1 mole). About 0.5 mole of hexa-hydroxymethyl melamineobtained above is dissolved in 150 grams ethanol and slowly addedthrough the dropping funnel. The temperature of the reaction mixture iscontrolled at 30° C. and the hexa-hydroxymethyl melamine is addeddropwise and mixed for 3 hours at 60° C. At the end of this period, theunreacted product and ethanol are separated by rotary evaporation widervacuum to obtain a diethanol melamine derivative.

The above obtained diethanol melamine derivative is dissolved in 100grams of dioxane or tetrahydrofuran (THF) and added drop wise to onemole of docosanoic acid chloride at 30° C. The mixture is heated to 50°C. and mixed for three hours. Later, the mixture is cooled to roomtemperature and the product is neutralized with 10% (weight %) sodiumbicarbonate. The solvent and water are evaporated and the fatty acidsalt is separated by extraction. The final product is re-dissolved,desalted and dried with molecular sieves to obtain the non-ionic geminisurfactant compound 6.

Example 3 Preparation of Compound 7

The hexa-hydroxymethyl melamine compound of Example 2 (1 mole) isdissolved in THF and added drop wise to two moles of a mixturecontaining 1:1 (weight by weight) docosanoic acid chloride and oxalicacid at 30° C., The mixture is heated to 70° C. and mixed for 2 hours,and later cooled to room temperature. The product is neutralized with10% (weight %) sodium bicarbonate, desalted and dried with molecularsieves. The product is evaporated by rotary evaporators and dried undervacuum to obtain the anionic gemini surfactant compound 7.

Example 4 Preparation of Compound 8

The hexa-hydroxymethyl melamine compound of Example 2 (1 mole) isdissolved in THF and added drop wise to two moles of a mixturecontaining 1:1 (weight by weight) docosanoic acid chloride andchlorosulfonic acid at 30° C. The mixture is heated to 70° C. and mixedfor 2 hours, and later cooled to room temperature. The product isneutralized with 10% (weight %) sodium bicarbonate, desalted and driedwith molecular sieves. The product is evaporated by rotary evaporatorsand dried under vacuum to obtain the sulfonate anionic gemini surfactantcompound 8.

Example 5 Preparation of Compound 9

The hexa-hydroxy methyl amine compound of Example 2 (1 mole) isdissolved in THF and added drop wise to two moles of a mixturecontaining 1:1 (weight by weight) docosanoic acid chloride andchlorophosphoric acid at 3° C. The mixture is heated to 70 and mixed foran additional 2 hours, and later cooled to room temperature. The productis neutralized with 10% (weight %) sodium bicarbonate, desalted anddried with molecular sieves. The product is evaporated by rotaryevaporators and dried under vacuum to obtain the phosphate anionicgemini surfactant compound 9.

Example 6 Preparation of Compound 10

The hydroxyl methyl melamine compound of Example 2 (0.5 mole) isdissolved in methanol and added drop wise to two moles of N,N-dimethylheneicosylamine at 30° C. The mixture is kept at 30 and mixed for twohours. The product is desalted and dried with molecular sieves. Theproduct is evaporated by rotary evaporators and dried under vacuum toobtain the cationic gemini surfactant compound 10.

Example 7 Preparation of Compound 11

A reaction vessel fitted with a condenser, a mechanical stirrer, and athermometer is heated in water bath at 65° C. and charged with 0.1 moleof novolac dissolved in 20% (weight %) sodium hydroxide solution. Thesolution is reacted with 0.5 mole of epichlorohydrin in the presence ofsodium hydroxide to obtain a novolac-chlorohydrin derivative. Thenovolac-chlorohydrin derivative is further reacted with 0.5 moletriethylamine, resulting in modification of chlorohydrin groups toquaternary ammonium hydroxides. The resulting product is further reactedwith 0.3 moles of docosyl chloride in the presence of a Friedel-Craftscatalyst (AlCl₃). The final product is evaporated by rotary evaporatorsand dried under vacuum to obtain the cationic gemini surfactant compound11.

Example 8 Preparation of Compound 12

A reaction vessel is charged with 0.1 mole of novolac dissolved in 20%sodium hydroxide solution. The reaction mixture is flushed with nitrogenand heated to 70° C. About 0.5 mole of sodium chloroacetate is addedslowly and mixed. The reaction is continued for one hour to ensure thatall the phenoxy groups are transferred to ether carboxylate groups. Theproduct obtained is alkylated with 0.5 mole of docosyl chloride in thepresence of a Friedel-Crafts catalyst (AlCl₃). The fit al product isevaporated by rotary evaporators and dried under vacuum to obtain thecarboxylate based anionic gemini surfactant compound 12.

Example 9 Preperation of Compound 13

A reaction vessel fitted with a condenser, a mechanical stirrer, and athermometer is heated in water bath at 65° C. and charged with 0.1 moleof novolac dissolved in 20% sodium hydroxide solution. The solution isreacted with 0.5 mole of epichlorohydrin in the presence of sodiumhydroxide to obtain a novolac chlorohydrin derivative. Further, thenovolac chlorohydrin derivative (0.3 mole) is added to an excess amountof diethanol amine at 70° C.; and the reaction is continued for one morehour. The excess of unreacted diethanolamine is separated and theproduct is alkylated by reacting with 0.5 mole of docosyl chloride inthe presence of a Friedel-Crafts catalyst. The final product isevaporated by rotary evaporators and dried under vacuum to obtain thegemini surfactant compound 11.

Example 10 Preparation of Compound 14

A reaction vessel fitted with a condenser, a dropping funnel, amechanical stirrer, and a thermometer is charged with 22.8 grams (0.1mole) of bisphenol-A, 8 grams of sodium hydroxide (as 20 weight %solution), and 0.3 mole of epichlorohydrin. About 0.6 mole offormaldehyde (as 37 weight % formalin solution) is added through thedropping funnel and mixed to form a tetramethylol bis-chlorohydrinderivative. The obtained product is mixed with an equimolar mixture ofN,N,N-trimethylamine and N,N,N-tri-dodecylamine and stirred for twohours at 25° C. The reaction is further continued at 50° C. for onehour. The final product is evaporated by rotary evaporators and driedunder vacuum to obtain the cationic gemini surfactant compound 14.

Example 11 Preparation of Compound 15

A reaction vessel fitted with a condenser, a dropping funnel, amechanical stirrer, and a thermometer is charged with 22.8 grams (0,1mole) of bisphenol-A, 8 grams of sodium hydroxide (as 20 weight %solution), and 0.3 mole of epichlorohydrin. About 0.6 mole offormaldehyde as 37 weight % formalin solution) is added through thedropping funnel and mixed to form a tetramethylol bis-chlorohydrinderivative. The obtained product is mixed with an equimolar mixture ofdiethanolamine and N,N,N-tri-dodecylamine and stirred for two hours at25° C. The reaction is further continued at 50° C. for one hour. Thefinal product is evaporated by rotary evaporators and dried under vacuumto obtain the gemini surfactant compound 15.

Example 12 Preparation of Compound 16

A reaction vessel fitted with a condenser, a dropping funnel, amechanical stirrer, and a thermometer is charged with 22.8 grams (0,1mole) of bisphenol-A, 8 grams of sodium hydroxide (as 20 weight %solution), and 0.3 mole of epichlorohydrin. About 0.6 mole offormaldehyde (as 37 weight % formalin solution) is added through thedropping funnel and mixed to form a tetramethylol bis-chlorohydrinderivative. The obtained product is mixed with an equimolar mixture ofN,N-disodium aminopropionate and N,N,N-tri-dodecylamine and stirred fortwc lours at 25° C. The reaction is further continued at 50° C., for onehour. The final product is evaporated by rotary evaporators and driedunder vacuum to obtain the carboxylate anionic gemini surfactantcompound 16.

Example 13 Preparation of Compound 17

About 34 grams (0.1 mole) of commercial liquid epoxy resin ofBisphenol-A epoxy resin is mixed with N,N,N-trimethylamine and stirredat 60° C. for one hour. The resulting product is added slowly tododecanoic acid chloride (0.2 mole) and further stirred for one hour at70° C. The final product is evaporated by rotary evaporators and driedunder vacuum to obtain the cationic gemini surfactant compound 17.

Example 14 Preparation of Compound 18

About 34 grams of commercial liquid epoxy resin of Bisphenol-A epoxyresin is added slowly to an equimolar mixture of N,N-diethanol amine andN,N,N-tri-dodecylamine, and mixed at 30° C. for one hour. The mixture isfurther heated to 100° C. for one hour. The final product is evaporatedby rotary evaporators and dried under vacuum to obtain the geminisurfactant compound 18.

Example 15 Preparation of Compound 19

About 34 grams of commercial liquid epoxy resin of Bispheno -A is addedslowly to an equimolar mixture of N,N-disodium aminopropionate andN,N,N-tri-dodecylamine, and mixed at 30° C. for one hour. The mixture isfurther heated to 100° C. for one hour. The final product is evaporatedby rotary evaporators and dried under vacuum to obtain the geminisurfactant compound 19.

Example 16 Preparation of Compound 20

A reaction vessel is charged with 22.8 grams (0.1 mole) of bisphenol-Aand 8 grams (0.2 mole) of sodium hydroxide (as 20 weight % solution),and heated to 65° C. About 4 mles of formaldehyde (as 37% w/w formalinsolution) is added and the reaction is continued at 65° C. for three hos, maintaining the pH at 9-10. The tetra-methylol bisphenol-A formed isreacted with mixture of 0.2 mole of diethanolamine and 0.2 mole ofN,N-didodecyl amine at ambient temperature, and then heated to 60° C.for two hours.

The product formed above is reacted with 0.2 mole of epichlorohydrin atpH 9-10 at 65° C. The epichlorohydrin derivative is added slowly to anequimolar mixture of N,N-diethanol amine and N,N,di-dodecylamine, andmixed at 30° C.; for one hour. The mixture is further heated to 100° C.for one hour. The final product is evaporated by rotary evaporators anddried under vacuum to obtain the gemini surfactant compound 20.

Example 17 Preparation of Compound 21

A reaction vessel is charged with 18 grams (0.1 mole) of resol dissolvedin 0.1 mole sodium hydroxide (as 20 weight % solution) and reacted with0.1 mole of epichlorohydrin at pH 9-10, and at temperature 65-70° C. Thereaction is continued for two hours with efficient mixing. Thechlorohydrin derivative obtained is reacted with an equimolar mixture ofN,N,N-triethylarnine and N,N,N-tri dodecylamine. The reaction is carriedout at 30° C. for two hours, and then further continued at 60° C., forone hour. The final product is evaporated by rotary evaporators anddried under vacuum to obtain the gemini surfactant compound 21.

Example 18 A Hydrophilic Paint with Surfactant

About 10 grams of compound 2 is mixed with 40 grams of TiO₂, 2 grams ofthickener (hydroxyethyl cellulose), 150 grams of solvent (water), 70grams of binder (methyl methacrylate), 0.3 grams of coalescing agent(2,2,4-trimethyl-1,3-pentanediolmono(2-methylpropanoate)), and 0.05grams of bactericide. The components are mixed wider high shear for 30minutes. The hydrophilic characteristics of the paint were investigatedand evaluated.

Example 19 A Hydrophilic Paint with Gemini Surfactant

About 10 grams of compound 14 is mixed with 40 grams of TiO₂, 2 grams ofthickener (hydroxyethyl cellulose), 150 grams of solvent (water), 70grams of binder (methyl methacrylate), 0.3 grams of coalescing agent(2,2,4-trimethyl-1,3-pentanediolmono(2-methylpropanoate)), and 0.05grains of bactericide. The components are mixed under high shear for 30minutes.

Example 20 Evaluation of Hydrophilic Property

The coating preparation of Example 18 is coated on a glass surface anddried at room temperature. The surface free energy and the water dropletcontact angle of the hydrophilic coating are measured as follows. AZisman plotting method is employed for measuring the surface freeenergy. The surface tension of various concentrations of the aqueoussolution of magnesium chloride is plotted along the X-axis, and thecontact angle in terms of cos θ is plotted along the Y-axis. A graph alinear relationship between the two is obtained. The graph isextrapolated such that the surface tension at contact angle 0° ismeasured and is defined as the surface free energy of the coated glasssurface. The surface free energy of the glass surface measured will be82 milliNewton/meter. The high surface free energy is indicative of thehydrophilic property of the coating.

Example 21 Evaluation of Hydrophilic Coating

A hydrophilic coating of Example 19 is coated on a glass substrate andevaluated for the following properties.

Hydrophilicity: The water droplet contact angle in air is measured byusing DropMaster 500 (Kyowa Interface Science Co., Ltd). The waterdroplet contact angle measured will be 7°. The low water droplet contactangle is indicative of the hydrophilic property of the coating.

Water resistance and Durability: The hydrophilic coating is subjected toa rubbing treatment with sponge in 10 reciprocations in water whileapplying a load of 1 kg. The amount of residual film is calculated froma change of weight before and after the rubbing treatment, The weight ofthe film after the rubbing treatment will be 97% of the initial weight.

Weather resistance: The hydrophilic coating is exposed in a chamber to axenon arc lamp that is calibrated to mimic the sun spectralcharacteristics (Atlas Sun Test). The exposure is performed for 500hours and evaluated with respect to hydrophilicity, water resistance anddurability. The hydrophilic coating will exhibit the same propertiesbefore and after the exposure.

In the above detailed description, reference is made to the accompanyingdrawings, which form a part hereof. In the drawings, similar symbolstypically identify similar components, unless context dictatesotherwise. The illustrative embodiments described in the detaileddescription, drawings, and claims are not meant to be limiting. Otherembodiments may be used, and other changes may be made, withoutdeparting from the spirit or scope of the subject matter presentedherein. It will be readily understood that the aspects of the presentdisclosure, as generally described herein, and illustrated in theFigures, can be arranged, substituted, combined, separated, and designedin a wide variety of different configurations, all of which areexplicitly contemplated herein.

The present disclosure is not to be limited in terms of the particularembodiments described in this application, which are intended asillustrations of various aspects. Many modifications and variations canbe made without departing from its spirit and scope, as will be apparentto those skilled in the art. Functionally equivalent methods andapparatuses within the scope of the disclosure, in addition to thoseenumerated herein, will be apparent to those skilled in the art from theforegoing descriptions. Such modifications and variations are intendedto fall within the scope of the appended claims. The present disclosureis to be limited only by the terms of the appended claims, along withthe full scope of equivalents to which such claims are entitled. It isto be understood that this disclosure is not limited to particularmethods, reagents, compounds, compositions or biological systems, whichcan, of course, vary. It is also to be understood that the terminologyused herein is for the purpose of describing particular embodimentsonly, and is not intended to be limiting.

As used in this document, the singular forms “a,” “an,” and “the”include plural references unless the context clearly dictates otherwise.Unless defined otherwise, all technical and scientific terms used hereinhave the same meanings as commonly understood by one of ordinary skillin the art. Nothing in this disclosure is to be construed as anadmission that the embodiments described in this disclosure are notentitled to antedate such disclosure by virtue of prior invention. Asused in this document, the term “comprising” means “including, but notlimited to.”

While various compositions, methods, and devices are described in termsof “comprising” various components or steps (interpreted as meaning“including, but not limited to”), the compositions, methods, and devicescan also “consist essentially of” or “consist of” the various componentsand steps, and such terminology should be interpreted as definingessentially closed-member groups.

With respect to the use of substantially any plural and/or singularterms herein, those having skill in the art can translate from theplural to the singular and/or from the singular to the plural as isappropriate to the context and/or application. The varioussingular/plural permutations may be expressly set forth herein for sakeof clarity.

It will be understood by those within the art that, in general, termsused herein, and especially in the appended claims (for example, bodiesof the appended claims) are generally intended as “open” terms Orexample, the term “including” should be interpreted as “including butnot limited to,” the term “having” should be interpreted as “having atleast,” the term “includes” should be interpreted as “includes but isnot limited to,” etc,). It will be further understood by those withinthe art that if a specific number of an introduced claim recitation isintended, such an intent will be explicitly recited in the claim, and inthe absence of such recitation no such intent is present. For example,as an aid to understanding, the following appended claims may containusage of the introductory phrases “at least one” and “one or more” tointroduce claim recitations, However, the use of such phrases should notbe construed to imply that the introduction of a claim recitation by theindefinite articles “a” or “an” limits any particular claim containingsuch introduced claim recitation to embodiments containing only one suchrecitation, even when the same claim includes the introductory phrases“one or more” or “at least one” and indefinite articles such as “a” or“an” (for example, “a” and/or “an” should be interpreted to mean “atleast one” or “one or more”): the same holds true for the use ofdefinite articles used to introduce claim recitations. In addition, evenif a specific number of an introduced claim recitation is explicitlyrecited, those skilled in the art will recognize that such recitationshould be interpreted to mean at least the recited number (for example,the bare recitation of “two recitations,” without other modifiers, meansat least two recitations, or two or more recitations). Furthermore, inthose instances where a convention analogous to “at least one of A, B,and C, etc.” is used, in general such a construction is intended in thesense one having skill in the art would understand the convention (forexample, “a system having at least one of A, B, and C” would include butnot be limited to systems that have A alone, B alone, C alone, A and Btogether, A and C together, B and C together, and/or A, B, and Ctogether, etc.). In those instances where a convention analogous to “atleast one of A, B, or C. etc.” is used, in general such a constructionis intended in the sense one having skill in the art would understandthe convention (for example, “a system having at least one of A, B. orC” would include but not be limited to systems that have A alone, Balone, C alone, A and B together, A and C together, B and C together,and/or A, B, and C together, etc.), It will be further understood bythose within the art that virtually any disjunctive word and/or phrasepresenting two or more alternative terms, whether in the description,claims, or drawings, should be understood to contemplate thepossibilities of including one of the terms, either of the terms, orboth terms. For example, the phrase “A or B” will he understood toinclude the possibilities of “A” or “B” or “A and B.”

In addition, where features or aspects of the disclosure are describedin terms of Markush groups, those skilled in the art will recognize thatthe disclosure is also thereby described in terms of any individualmember or subgroup of members of the Markush group.

As will be understood by one skilled in the art, for any and allpurposes, such as in terms of providing a written description, allranges disclosed herein also encompass any and all possible subrangesand combinations of subranges thereof. Any listed range can be easilyrecognized as sufficiently describing and enabling the same range beingbroken down into at least equal halves, thirds, quarters, fifths,tenths, etc. As a non-limiting example, each range discussed herein canbe readily broken down into a lower third, middle third and upper third,etc. As will also be understood by one skilled in the art all languagesuch as “up to,” “at least,” and the like include the number recited andrefer to ranges which can be subsequently broken down into subranges asdiscussed above. Finally, as will be understood by one skilled in theart, a range includes each individual member. Thus, for example, a grouphaving 1-3 cells refers to groups having 1, 2, or 3 cells. Similarly, agroup having 1-5 cells refers to groups having 1, 2, 3, 4, or 5 cells,and so forth.

Various of the above-disclosed and other features and functions, oralternatives thereof, may be combined into many other different systemsor applications. Various presently unforeseen or unanticipatedalternatives, modifications, variations or improvements therein may besubsequently made by those skilled in the art, each of which is alsointended to be encompassed by the disclosed embodiments.

What is claimed is:
 1. A compound of formula I:

wherein A¹ is —H, —N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂,—NH—CH₂—CH₂—OH, —N⁺(CH₂—CH₂—OH)₃.X⁻, —O—Z—CH₃, —N⁺[Z—CH₃]₃.X⁻,—O—C(═O)—COO⁻.Na⁺, —N⁺(—CH₃)₂—Z—CH₃.X⁻, or salt thereof; A² is —H,—N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH,—N⁺(CH₂—CH₂—OH)₃.X⁻, —O—Z—CH₃, —N⁺(Z—CH₃)₃.X⁻, —O—C(═O)—COO⁻.Na⁺,—N⁺(—CH₃)₂—Z—CH₃.X⁻, or salt thereof; A³ is —N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂,—N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH, —N⁺(CH₂—CH₂—OH)₃.X⁻, —O—Z—CH₃,—N⁺(Z—CH₃)₃.X⁻, —O—C(═O)—COO⁻.Na⁺, —N⁺(—CH₃)₂—Z—CH₃.X⁻, or salt thereof;A⁴ is —N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH,—N⁺(CH₂—CH₂—OH)₃.X⁻, —O—Z—CH₃, —N⁺(Z—CH₃)₃.X⁻, —O—C(═O)—COO⁻.Na⁺,—N⁺(—CH₃)₂—Z—CH₃.X⁻, or salt thereof; each Z is, independently, C₁-C₂₅alkylene, C₁-C₂₅ substituted alkylene, C₆-C₂₅ arylene, C₆-C₂₅substituted arylene, C₂-C₂₅ alkenylene, C₂-C₂₅ substituted alkenylene,C₂-C₂₅ alkynylene, C₂-C₂₅ substituted alkynylene, or absent; Q is—C(═O)—, —CH₂—CH₂—, —CH₂—(CH₂)_(k)—CH₂—, —C(═O)—NH—C(═O)—, or polyurea,where k is an integer from 1 to 10; and X is Cl, Br, F, I, or OH; andwherein two of A¹, A², A³, or A⁴ are hydrophilic groups selected from—H, —N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂, —N⁺H₃.X⁻—NH—CH₂—CH₂—OH, —N⁺(CH₂—CH₂—OH)₃.X⁻,—N⁺[Z—CH₃]₃.X⁻, —O—C(═)—COO⁻.Na⁺, —N⁺(—CH₃)₂—Z—CH₃.X⁻, or salt thereof,and other two of A¹, A², A³, or A⁴ are hydrophobic groups selected from—N[Z—CH₃]₂ and —O—Z—CH₃.
 2. The compound of claim 1, wherein A¹ is —H,—N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH,—N⁺(CH₂—CH₂—OH)₃.X⁻, or —O—Z—CH₃.
 3. The compound of claim 1, wherein A²is —H, —N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH,—N⁺(CH₂—CH₂—OH)₃.X⁻, or —O—Z—CH₃.
 4. The compound of claim 1, wherein A³is —N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH,—N⁺(CH₂—CH₂—OH)₃.X⁻, or —O—Z—CH₃.
 5. The compound of claim 1, wherein A⁴is —N[CH₂—N⁺(Z—CH₃)₃.X⁻]₂, —N⁺H₃.X⁻, —N[Z—CH₃]₂, —NH—CH₂—CH₂—OH,—N⁺(CH₂—CH₂—OH)₃.X⁻, or —O—Z—CH₃.
 6. The compound of claim 1, wherein:A¹ is —N[Z—CH₃]₂ or —O—Z—CH₃; A² is —N[Z—CH₃]₂ or —O—Z—CH₃; A³ is—N[CH₂—N⁺(CH₃)₃.Br⁻]₂ or —N⁺(Z—CH₃)₃.Br⁻; A⁴ is —N[CH₂—N⁺(CH₃)₃.Br⁻]₂ or—N⁺(Z—CH₃)₃.Br⁻; and Q is —C(═O)— or —CH₂—(CH₂)_(k)—CH₂—.
 7. Thecompound of claim 1, wherein A¹ is —N[Z—CH₃]₂, A² is —N[Z—CH₃]₂, A³ is—N[CH₂—N⁺(CH₃)₃.Br⁻]₂, A⁴ is —N[CH₂—N⁺(CH₃)₃.Br⁻]₂, and Q is —C(═)—. 8.The compound of claim 1, wherein A¹ is —O—C(═O)—COO⁻.Na⁺, A² is—O—Z—CH₃, A³ is —O—C(═O)—COO⁻.Na⁺, A⁴ is —O—Z—CH₃, and Q is —C(═O)—. 9.The compound of claim 1, wherein A¹ is —N⁺(Z—CH₃)₃.Br⁻, A² is —O—Z—CH₃,A³ is —N⁺(Z—CH₃)₃.Br⁻, A⁴ is —O—Z—CH₃, and Q is —C(═O)—.